RIZAL TECHNOLOGICAL UNIVERSITY

Maybunga, Pasig City

MATERIALS SCIENCE AND ENGINEERING

“POLYMERS”

SUBMITTED BY: SUBMITTED TO:

DERILO, ROSALIE ENGR. PAUL ADRIAN C. MANALANG

LABALAN, MIDY KARL
MAKITID, BRENDAN FRASTER
MEDINA, ASHLEY QUEEN
MERIALES, KIMURA
QUITEBES, LYKA ANGELA
TROYO, MA. ERIKA

PCEIT-29- 201P
SAT/10:30A- 1:30P
WRITTEN REPORTS
 4.4 THE CHEMISTRY OF POLYMER MOLECULES

Consider again the hydrocarbon ethylene (C2H4), which is a gas at ambient

temperature and pressure, and has the following molecular structure:

If the ethylene gas is subjected catalytically to appropriate conditions of temperature

and pressure, it will transform to polyethylene (PE), which is a solid polymeric material.
This process begins when an active mer is formed by the reaction between an initiator
or catalyst species (R) and the ethylene mer unit, as follows:

The polymer chain then forms by the sequential addition of polyethylene monomer units
to this active initiator-mer center. 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:

When all the repeating units along a chain are of the same type, the resulting polymer is
called a homopolymer. There is no restriction in polymer synthesis that prevents the
formation of compounds other than homopolymers; and, in fact, chains may be
composed of two or more different mer units, in what are termed copolymers.

The monomers discussed thus far have an active bond that may react to covalently
bond with other monomers, as indicated above for ethylene; such a monomer is termed
bifunctional; that is, it may bond with two other units in forming the two-dimensional
chainlike molecular structure. However, other monomers, such as phenol-formaldehyde
are trifunctional; they have three active bonds, from which a three-dimensional
molecular network structure results.
 4.5 MOLECULAR WEIGHT

‘‘Molecular mass,’’ ‘‘molar mass,’’ and ‘‘relative molecular mass’’ are sometimes used
and are really more appropriate terms than ‘‘molecular weight’’ in the context of the
present discussion—in actual fact, we are dealing with masses and not weights.
However, molecular weight is most commonly found in the polymer literature, and thus
will be used throughout this discussion.

Extremely large molecular weights1 are to be found in polymers with very long chains.
During the polymerization process in which these large macromolecules are
synthesized from smaller molecules, not all polymer chains will grow to the same length;
this results in a distribution of chain lengths or molecular weights. Ordinarily, an average
molecular weight is specified, which may be determined by the measurement of various
physical properties such as viscosity and osmotic pressure.

There are several ways of defining average molecular weight. The numberaverage
molecular weight Mn is obtained by dividing the chains into a series of size ranges and
then determining the number fraction of chains within each size range.

Number-Average Molecular Weight

The numberaverage molecular weight Mn is obtained by dividing the chains into a

series of size ranges and then determining the number fraction of chains within each
size range.

where Mi represents the mean (middle) molecular weight of size range i, and xi is the
fraction of the total number of chains within the corresponding size range.

Weight-Average Molecular Weight

It is based on the weight fraction of molecules within the various size ranges
where, again, Mi is the mean molecular weight within a size range, whereas wi denotes
the weight fraction of molecules within the same size interval.

An alternate way of expressing average chain size of a polymer is as the degree of

polymerization n, which represents the average number of mer units in a chain.

Both number-average (nn) and weight-average (nw) degrees of polymerization are

possible, as follows:

where Mn and Mw are the number-average and weight-average molecular weights as

defined above, while m is the mer molecular weight. For a copolymer (having two or
more different mer units), m is determined from:

In this expression, fj and mj are, respectively, the chain fraction and molecular weight of
mer j.
4.6 MOLECULAR SHAPE

There is no reason to suppose that polymer chain molecules are strictly straight,
in the sense that the zigzag arrangement of the backbone atoms is disregarded. Single
chain bonds are capable of rotation and bending in three dimensions. The chain atoms
in a third carbon atom may lie at any point on the cone of revolution and still subtend
about a 109 angle with the bond between the other two atoms. A straight chain segment
results when successive chain atoms are positioned. On the other hand, chain bending
and twisting are possible when there is a rotation of the chain atoms into other
positions.

A single chain molecule composed of many chain atoms might assume a shape
similar to that represented schematically, having a multitude of bends, twists, and kinks.
Also, the end-to-end distance of the polymer chain r; this distance is much smaller than
the total chain length.

Polymers consist of large numbers of molecular chains, each of which may bend,
coil, and kink in the manner. This leads to extensive intertwining and entanglement of
neighboring chain molecules, a situation similar to that of a fishing line that has
experienced backlash from a fishing reel. These random coils and molecular
entanglements are responsible for a number of important characteristics of polymers, to
include the large elastic extensions displayed by the rubber materials.

Some of the mechanical and thermal characteristics of polymers are a function of

the ability of chain segments to experience rotation in response to applied stresses or
thermal vibrations. Rotational flexibility is dependent on mer structure and chemistry.

For example, the region of a chain segment that has a double bond (CuC) is rotationally
rigid. Also, introduction of a bulky or large side group of atoms restricts rotational
movement.

For example, polystyrene molecules, which have a phenyl side group, are more
resistant to rotational motion than polyethylene chains.
Schematic representations of how polymer chain shape is influenced by the positioning
of backbone carbon atoms (solid circles). For (a), the rightmost atom may lie anywhere
on the dashed circle and still subtend a 109 angle with the bond between the other two
atoms. Straight and twisted chain segments are generated when the backbone atoms
are situated as in (b) and (c), respectively. (From Science and Engineering of Materials,
3rd edition, by D. R.Askeland.  1994. Reprinted with permission of Brooks/Cole, a
division of Thomson Learning. Fax 800 730-2215.)

Schematic representation of a single

polymer chain molecule that has numerous
random kinks and coils produced by chain
bond rotations. (From L. R. G. Treloar, The
Physics of Rubber Elasticity, 2nd edition,
Oxford University Press, Oxford, 1958, p. 47.)

4.7 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. Modern
polymer synthesis techniques permit considerable control over various structural
possibilities.

LINEAR POLYMERS

Linear polymers are those in which the mer units are joined together end to end in
single chains. These long chains are flexible and may be thought of as a mass of
spaghetti, where each circle represents a mer unit. For linear polymers, there may be
extensive van der Waals and hydrogen bonding between the chains. Some of the
common polymers that form with linear structures are polyethylene, polyvinyl chloride,
polystyrene, polymethyl methacrylate, nylon, and the fluorocarbons.

BRANCHED POLYMERS

Polymers may be synthesized in which side-branch chains are connected to the main
ones, these are fittingly called branched polymers. The branches, considered to be part
of the main-chain molecule, result from side reactions that occur during the synthesis of
the polymer. The chain packing efficiency is reduced with the formation of side
branches, which results in a lowering of the polymer density. Those polymers that form
linear structures may also be branched

Schematic representations of (a) linear, (b) branched, (c) crosslinked, and (d) network
(three-dimensional) molecular structures. Circles designate individual mer units.
CROSSLINKED POLYMERS

In crosslinked polymers, adjacent linear chains are joined one to another at various
positions by covalent bonds. The process of crosslinking is achieved either during
synthesis or by a nonreversible chemical reaction that is usually carried out at an
elevated temperature. Often, this crosslinking is accomplished by additive atoms or
molecules that are covalently bonded to the chains. Many of the rubber elastic materials
are crosslinked; in rubbers, this is called vulcanization.

NETWORK POLYMERS

Trifunctional mer units, having three active covalent bonds, form three-dimensional
networks and are termed network polymers. Actually, a polymer that is highly
crosslinked may be classified as a network polymer. These materials have distinctive
mechanical and thermal properties; the epoxies and phenol-formaldehyde belong to this
group. It should be pointed out that polymers are not usually of only one distinctive
structural type. For example, a predominantly linear polymer might have some limited
branching and crosslinking.

4.8 MOLECULAR CONFIGURATION

Polymer molecules can be explained through molecular size, molecular shape ,and
molecular structure. Molecular size is a measure of the area a molecule occupies in
three-dimensional space. The amount of space any mass takes up in three-dimensional
space is known specifically as its volume. The three dimensional shape or configuration
of a molecule is an important characteristic. This shape is dependent on the preferred
spatial orientation of covalent bonds to atoms having two or more bonding partners.
Three dimensional configurations are best viewed with the aid of models. In order to
represent such configurations on a two-dimensional surface (paper, blackboard or
screen), we often use perspective drawings in which the direction of a bond is specified
by the line connecting the bonded atoms. Molecular structure can be linear, branched,
crosslinked ,and network structure.

MOLECULAR CHARACTERISTICS

CHEMISTRY SIZE SHAPE STRUCTURE

mer composition (molecular weight) (chain twisting, Linear
entanglement, and Branched
 etc. Crosslinked
Network

Branched and linear are isomeric states. Isomeric stare is subcategorized into two:
Sterecisomers (Isotactic, Syndiotactic ,Atactic) and geometrical isomers (cis, trans).

4.9 THERMOPLASCTIC AND THERMOSETTING POLYMERS

The response of a polymer to mechanical forces at raised temperature is
interconnected to its dominant molecular structure. And, in fact one classification
scheme for these materials is according to behavior with rising
temperature.Thermoplasts (or thermoplastic polymers) and thermosets (or
thermosetting polymers,) are the two subdivisions.A polymer is simply a material
composed of many repeated units called monomers that link together into chains or
branches. Some polymers like starch, cellulose and rubber occur naturally while
others like polyester, nylon and plastic are synthetic. The monomers that make up
thermoplastic polymers come together via electrical bonds called van der Waals
forces that weakly attract neutral molecules to each other. These repeating units
arrange themselves in such a way that thermoplastic polymer molecules look like
many strands of pearls mixed together. denoting substances (especially synthetic
resins) that become plastic on heating and harden on cooling, and are able to repeat
these processes. There are actually many types of thermoplastic polymers, which are
unique in form and function. Manufacturers often use high pressure polyethylene to
encapsulate rigid objects like electrical equipment. Low pressure polyethylene is very
elastic and ideal for insulating electrical cables. Polyamide is most commonly
associated with the production of ropes and belts. Perhaps the most readily
recognizable thermoplastic polymer is polyvinyl chloride, or PVC, which readily molds
into pipes, containers and insulation materials. Finally, some adhesives are
thermoplastic polymers, including acrylates, cyanoacrylates and epoxy. A
thermosetting polymer which is also known as a thermoset or thermosetting plastic is a
polymer consisting of cross-linked structure or heavily branched molecules.
Common examples of thermoset plastics and polymers include epoxy, silicone,
polyurethane and phenolic. In addition, some materials such as polyester can occur in
both thermoplastic and thermoset versions.

4.10 COPOLYMERS

Polymer chemists and scientists are continually finding new materials that can be easily,
economically synthesized, and invented with progress properties or better combinations
than are offered by the homo polymers heretofore discussed. One group of these
materials are copolymers Homo polymers are polymeric molecules in which one type
of chemical repeat unit or monomer is repeated many times (typically >1000) to produce
a linear macromolecule of high molecular weight. Consider a copolymer that is
composed of two mer units as represented by black and red small circles. Depending
on polymerization process and the relative fractions of these mer types, different
sequencing arrangements along the polymer chains are possible. There are examples
of copolymers below.

POLYMER STRUCTURES

A random copolymer is one in which the monomer residues are located randomly in the
polymer molecule. An example is the copolymer of vinyl chloride and vinyl acetate,
made by free-radical copolymerization. An alternating copolymer is
a copolymer comprising two species of monomeric units distributed
in alternating sequence. A block copolymer is a copolymer formed when the two
monomers cluster together and form 'blocks' of repeating units. For example,
a polymer made up of X and Y monomers joined together like: -Y-Y-Y-Y-Y-X-X-X-X-X-
Y-Y-Y-Y-Y-X-X-X-X-X- is a block copolymer where -Y-Y-Y-Y-Y- and -X-X-X-X-X- groups
are the blocks. Graft copolymer is a type of copolymer in which one or more blocks of
homo polymer are grafted as branches onto a main chain, meaning it is a
branched copolymer with one or more side chains of a homo polymer attached to the
backbone of the main chain.
REFERENCES:
Molecular size. Retrieved from :https://sciencing.com/calculate-molecular-size-
6641003.html
Molecular Retrieved from
shape.https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modul
es_(Organic_Chemistry)/Fundamentals/Introduction_to_Organic_Chemistry/Molecular_
Shape
THERMOPLASTIC .Retrieved from: .https://sciencing.com/thermoplastic-polymer-
5552849.html
Thermosetting. Retrieved from :https://byjus.com/chemistry/thermosetting-polymers/
Homo polymers. Retrieved
from :https://www.sciencedirect.com/topics/engineering/homopolymers

FIGURE 4.13
The chain-folded structure
for a plateshaped polymer
crystallite.

FIGURE 4.14
Schematic representation
of the detailed structure of a spherulite.
(From John C. Coburn, Dielectric Relaxation
Processes in Poly(ethylene terephthalate),
Dissertation, University of Utah, 1984.)

The detailed structure of a spherulite is illustrated schematically in Figure 4.14; shown

here are the individual chain-folded lamellar crystals that are separated by amorphous
material. Tie-chain molecules that act as connecting links between adjacent lamellae
pass through these amorphous regions. As the crystallization of a spherulitic structure
nears completion, the extremities of adjacent spherulites begin to impinge on one
another, forming more or less planar boundaries; prior to this time, they maintain their
spherical shape.

FIGURE 4.15
A transmission photomicrograph
(using cross-polarized light)
showing the spherulite structure of polyethylene.
Linear boundaries form between adjacent spherulites,
and within each spherulite appears a Maltese cross. 525.
(Courtesy F. P. Price, General Electric Company.)
These boundaries are evident in Figure 4.15, which is a photomicrograph of
polyethylene using cross-polarized light. A characteristic Maltese cross pattern appears
within each spherulite. Spherulites are considered to be the polymer analogue of grains
in polycrystalline metals and ceramics. However, as discussed above, each spherulite is
really composed of many different lamellar crystals and, in addition, some amorphous
material. Polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene, and
nylon form a spherulitic structure when they crystallize from a melt.

SUMMARY

Most polymeric materials are composed of very large molecules—chains of

carbon atoms, to which are side-bonded various atoms or radicals. These
macromolecules may be thought of as being composed of mers, smaller structural
entities, which are repeated along the chain. Mer structures of some of the chemically
simple polymers (e.g., polyethylene, polytetrafluoroethylene, polyvinyl chloride, and
polypropylene) were presented. Molecular weights for high polymers may be in excess
of a million. Since all molecules are not of the same size, there is a distribution of
molecular weights. Molecular weight is often expressed in terms of number and weight
averages. Chain length may also be specified by degree of polymerization, the number
of mer units per average molecule.

IMPORTANTTERMSANDCONCEPTS

Alternating copolymer Block copolymer

Atactic configuration Branched polymer
Bifunctional mer Chain-folded model Cis (structure)
Copolymer Crosslinked polymer
Crystallite Degree of polymerization
Graft copolymer
Homopolymer
Isomerism
Isotactic configuration
Linear polymer
Macromolecule
Mer
Molecular chemistry
Molecular structure
Molecular weight
Monomer Network polymer
Polymer
Polymer crystallinity
Random copolymer
Saturated
Spherulite
Stereoisomerism
Syndiotactic configuration
Thermoplastic polymer
Thermosetting polymer
Trans (structure)
Trifunctional mer
Unsaturated
 REFERENCES

Baer, E., ‘‘Advanced Polymers,’’ Scientific American, Vol. 255, No. 4, October
1986, pp. 178–190. Bovey, F. A. and F. H. Winslow (Editors), Macromolecules: An
Introduction to Polymer Science, Academic Press, New York, 1979. Cowie, J. M. G.,
Polymers: Chemistry and Physics of Modern Materials, 2nd edition, Chapman and Hall
(USA), New York, 1991. Engineered Materials Handbook, Vol. 2, Engineering Plastics,
ASM International, Materials Park, OH, 1988. McCrum, N. G., C. P. Buckley, and C. B.
Bucknall,

Principles ofPolymer Engineering,2nd edition, Oxford University Press, Oxford,

1997. Chapters 0–6. Rodriguez, F., Principles of Polymer Systems, 3rd edition,
Hemisphere Publishing Company (Taylor & Francis), New York, 1989. Rosen, S. L.,
Fundamental Principles of Polymeric Materials, 2nd edition, John Wiley & Sons, New
York, 1993. Rudin, A., The Elements of Polymer Science and Engineering: An
Introductory Text for Engineers and Chemists, Academic Press, New York, 1982.
Questions and Problems

To solve those problems having an asterisk (*) by their numbers, consultation of

supplementary topocs [appearing only on yhe CD-ROM (and not in print)] will probably
be necessary.
Polymers problems are always have questions to solve. Polymers structures are given
to able to have a guide when solving a problem to prevent us from struggling on what
we are solving. On this we compute the different moleculat weight like polyvinyl
chloride, polyethylene, polycarbonate and polydimethylsiloxane.

◙Below, molecular weight data for a polypropylene material are tabulated. Compute:
A. the number-average molecular weight,
B. the weight-average molecular weight,
C. The number-average degree of polymerzation.
D. the weight-average degree of polymerization.

◙Below, molecular weight data for some polymer are tabulated. Compute:
A. The number-average molecular weight
B. The weight-average molecular weight
C. Material weight average degree
D. What is the material's number average degree of polymerisation.

◙Is it possible to have a polymethyl methacrylate homopolymer with the following

molecular weight data.
◙For a linear polymer molecule, the total chain length L depends on the bond length
between chain atoms d, the total number of bonds in the molecule N, and the angle
between adjacent backbone chain atoms as follows:

◙Furthermore, the average end-to-end distance for a series of polymer molecules r in.

◙The density of totally crystalline polypropylene at room temperature is 0.946 g/cm3.

◙If the volume of a monoclinic unit cell, Vmono is a function of these lattice parameters.

◙The density and associated percent crystallinity for two polytetrafluoroethylene

materials are as follows.

A. Compute the densities of totally crystal-line and totally amorphous

polytetrafluoroethylene.
B. Determine the percent crystallinity of a specimen having a density of 2.26
g/cm3.

◙The density and associated percent crystallinity for two nylon 6,6 materials are as
follows:
 A.Compute the densities of totally crystalline and totally amorphous nylon 6,6.
B. Determine the density of a specimen having 55.4% crystallinity.

Molecular Configuration

◙For polymers having more than one side atom or group of atoms bonded to the main
chain.

◙In which R represents an atom or side group other than hydrogen (e.g., Cl, CH3)

◙This is designated as a head-to-tail configuration.

Stereoisomerism

◙Stereoisomerism denotes the situation in which atoms are linked together in the same
order (head-to-tail) but differ in their spatial arrangement.

◙This is called an isotactic configuration. In a syndiotactic configuration, the R groups

alternate sides of the chain:
◙And for random positioning,

Geometrical Isomerism
◙Other important chain configurations, or geometrical isomers, are possible within mer
units having a double bond between chain carbon atoms. Bonded to each of the carbon
atoms participating in the double bond is a single side-bonded atom or radical, which
may be situated on one side of the chain or its opposite.

◙in which the CH3 group and the H atom are positioned on the same side of the chain.
This is termed a cis structure, and the resulting polymer, cis-polyisoprene.