Subject Code Chem 3 Reactions and Interactions of Organic and Inorganic Compounds

Module Code 5.0 Biomolecules II

Lesson Code 5.10 Classifications and Properties of Polymers
Time Limit 30 minutes

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Components Tasks TA a
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b

Target The target of this learning guide is to: 0.5

1) Summarize the factors affecting the classifications and properties of min
polymers based on data gathered from research and/or journal articles.
1.5
Hook Despite their size, polymers have chemical and physical properties that can be min
described using what we currently know about their monomers. We can
describe the physical properties of polymers using principles we've already
learned. Despite the fact that polymers do not crystallize or melt as well as
smaller molecules, we can discover crystalline areas in polymers and
determine the temperatures at which these crystallites melt (Wade, 2013).
Polymers are not, however, liquids or crystalline solids with a low melting
point, as low molecular weight compounds in traditional organic chemistry
are. Instead, they take on a range of physical shapes, such as oils, rubbers, and
brittle glasses, as well as soft and flexible solids. The underlying molecular
structure of these materials can be used to describe their physical properties,
at least in general terms (Nicholson, 2006). In this learning guide, some
classifications and properties of polymers are discussed.
18
Ignite 1. Classification based on type of monomer unit min
(Klein, 2017)

1.1 Homopolymers: They are polymers formed from one kind of monomer.
Illustration:

1.2 Copolymer or mixed polymers: They are polymers formed from more
than one kind of monomer unit.

1.2.1 Alternating copolymers: They have a recurring unit distribution that

alternates.
Illustration:

1.2.2 Random copolymers: They have a random distribution of repeated

units.
Illustration:

Chem 3 LG 5.10 Biomolecules II: Classifications and Properties of Polymers Page 1 of 7

 1.2.3 Block copolymers: Different homopolymer subunits are linked together
in a single chain.
Illustration:

1.2.4 Graft copolymers: They comprise grafting parts of one homopolymer

into the chain of another homopolymer.
Illustration:

2. Classification based upon origin or source

(Agarwal, 2017)

2.1 Natural polymers: They are polymers that can be naturally found (i.e. in
plants and in animals).
Example: Starch, cellulose, protein, Nucleic acids, natural rubber, etc.

2.2 Synthetic polymers: They are man-made polymers synthesized in the

laboratory from low molecular weight compounds.
Example: Nylon, Dacron, Bakelite, synthetic rubber, polystyrene, etc.

2.3 Semi-synthetic polymers: Chemical alterations are used to create them,

which are generally sourced from naturally occurring polymers.
Example: The acid-catalyzed reaction between cellulose and acetic anhydride
produces cellulose diacetate. Films, threads, and glasses are all made from
cellulose diacetate.

3. Classification based on structure

(Karty, 2018; Klein, 2017)

3.1 Linear polymers: Monomer units are joined together to create long
straight chains in these polymers. To create a well-packed structure, the
polymeric chains are piled on top of one another. High density, tensile
strength, and melting points characterize these polymers.
Example: Polyethylene, Nylon and polyesters
Illustration:

Chem 3 LG 5.10 Biomolecules II: Classifications and Properties of Polymers Page 2 of 7

 3.2 Branched chain polymers: They are polymers made up of
monomer units joined together to form the lengthy main chain. The branches
are made up of side chains of various lengths. The packing of branched chain
polymers is uneven. In comparison to linear polymers, these polymers have
lower tensile strength and melting temperatures.
Example: Amylopectin in starch
Illustration:

3.3 Cross linked polymers: They are polymers that are made up of
monomer units joined together to form a 3-D network. Because of their
network structure, cross-linked polymers are stiff, inflexible, and brittle.
Example: Bakelite
Illustration:

4. Classification based on synthesis or mode of assembly

(Agarwal, 2017)

4.1 Addition polymerization: It incorporates the self-addition of many one

or two unsaturated monomers to generate a single large molecule without the
loss of any tiny molecules. The product is called as an addition polymer.
Example: Polyethylene

4.2 Condensation polymerization: By eliminating a tiny molecule like H2O

or CH3OH as a by-product, the monomer (may be the same or different
monomers) units bond with each other. The product is called as a condensation
polymer. Condensation polymerization is also known as step polymerization
because it involves stepwise intermolecular condensation. The product is
called as a step growth polymer.
Example: Nylon, terylene, etc.

Chem 3 LG 5.10 Biomolecules II: Classifications and Properties of Polymers Page 3 of 7

 5. Classification by reaction type of addition polymers
(Wade, 2013)

5.1 Free-radical polymerization: It is a chain-growth polymerization

process that involves a free radical at the end of the developing chain to
generate an addition polymer.
Example:

5.2 Cationic polymerization: It is a chain-growth polymerization method

that involves a cation at the end of the extending chain to produce an addition
polymer. It needs a monomer that forms a relatively stable carbocation when
it reacts with the cationic end of the growing chain. The process is favored
when the monomer contains an electron-donating group that can stabilize the
carbocation intermediate.
Example:

5.3 Anionic polymerization: An anion at the end of the developing chain is

used in the process of generating an addition polymer by chain-growth
polymerization. It requires a monomer that gives a stabilized carbanion when
it reacts with the anionic end of the growing chain. The process is favored if
the monomer contains an electron-withdrawing group (e.g. carbonyl group,
cyano group, or nitro group) that can stabilize the carboanion intermediate.
Example:

6. Classification based on stereochemistry of addition polymers

(Wade, 2013)

6.1 Isotactic polymer: All of the side groups are on the same side of the
polymer backbone in this polymer.

Chem 3 LG 5.10 Biomolecules II: Classifications and Properties of Polymers Page 4 of 7

 6.2 Syndiotactic polymer: The side groups are on opposite sides of the
polymer backbone in this polymer.

6.3 Atactic polymer: A polymer having side groups on the polymer backbone
at random locations.

7. Classification based on intermolecular forces present

(Smith, 2011; Agarwal, 2017)

7.1 Elastomers: They are polymers having elastic character. The weakest
intermolecular forces hold the polymer chains together in this type of polymer
and allow the polymer to be stressed and stretched, but the polymer regains its
former shape when the stress is relieved. The elasticity of such polymers can
be further modified by introducing few cross links between the chains.
Example: Natural rubber

7.2 Fibers: Very strong intermolecular forces like hydrogen bonding are
present in these polymers. They have high modulus and tensile strength. They
are polymers that look like threads.
Example: Nylon, Dacron etc.

7.3 Thermoplastics: These are polymers that can be easily molded into
other shapes after being heated and then cooled to room temperature.
Thermoplastic polymers have intermolecular forces that are midway between
elastomers and fibers. Thermoplastic polymers soften and become fluids
when heated, but harden when cooled.
Example: Polyethylene, Polystyrene

7.4 Plasticizers: The addition of some organic molecules known as

plasticizers can easily soften other materials. The plasticizing effect is caused
by solubilization and the resulting decrease in intermolecular forces, which
allows molecules to move freely relative to one another.
Examples: Tricresyl phosphate, Dimethyl phthalate, Triphenyl phosphate,
Camphor

7.5 Thermosetting polymers: Heating causes these polymers to harden and

become infusible. Excessive cross-linking between chains occurs during
heating, resulting in a 3-D network of bonds.
Example: Bakelite

Chem 3 LG 5.10 Biomolecules II: Classifications and Properties of Polymers Page 5 of 7

 8. Properties of polymers
(Wade, 2013)

8.1 Polymer crystallinity: It refers to the amount of polymer present in

crystallites as well as the sizes of those crystallites. Crystallites are small
crystalline areas found within a solid polymer at temperatures below
crystalline melting (Wade, 2013). It is also the part of a polymer where the
chains are linearly extended and close together, generating van der Waals
forces that hold them together (Klein, 2017).
8.1.1 Amorphous polymers: They are polymers with long chains and low
crystallinity.

8.1.2 Crystalline polymers: They are polymers with long chains and high
crystallinity.

8.2 Thermal properties: Long-chain polymers exist as glasses at low

temperatures. They are rigid and inflexible. They can be fractured by a forceful
impact. The polymer goes through a Tg as the temperature rises. The polymer
achieves the Tm as the temperature is increased further.

8.2.1 Glass transition temperature (Tg): It is the point at which a highly

crystalline polymer becomes rubbery, flexible, or moldable when heated over
a certain temperature. The term thermoplastic refers to a polymer that
becomes plastic when heated.

8.2.2 Melt transition temperature (Tm) or crystalline melting temperature:

It is the point at which the crystallites in a highly crystalline polymer
melt. Crystallites melt at this temperature, allowing individual molecules to
flow past one another. The polymer is a liquid with high viscosity above
the Tm.

8.3 Solubility: The polymer appears to dissolve when the intermolecular

interactions in between solvent molecules and the polymer molecules are
similar. Any variables that limit interactions between the solvent molecules
and the polymer will diminish solubility. Because the cross-links prevent
enough interactions between the solvent and the polymer, network polymers
are rarely soluble. Because solvent–polymer interactions may not be strong
enough to overcome polymer–polymer interactions, highly crystalline
polymers have low solubility (Karty, 2018).
8
Navigate Polymers have a wide range of classifications which determine their eventual min
applications or uses. Some of the classifications of polymers are based
on/upon the:
1) type of monomer unit
2) origin or source
3) structure
4) synthesis or mode of assembly
5) reaction type of addition polymers
6) stereochemistry of addition polymers
7) intermolecular forces present

Chem 3 LG 5.10 Biomolecules II: Classifications and Properties of Polymers Page 6 of 7

 Together with these classifications, polymers also possess a wide range of
properties. Some of these are:
1) polymer crystallinity
2) thermal properties
3) solubility

2
NOTE TO THE TEACHER: This is just a suggested alternative activity/ min
Knot assessment tool that may or may not be accomplished.

Search and download one (1) reviewed article/journal that involves a synthesis
of a certain polymer. Describe its classification/s based on the classifications
(whichever is applicable) that are listed down in this learning guide.
a – suggested time allocation set by the teacher
b – actual time spent by the student (for information purposes only)

References:
Agarwal, R. (2017). Organic chemistry for JEE. McGraw Hill Education (India).
Karty, J. (2018). Organic chemistry: Principles and mechanisms (2nd ed.). W. W. Norton &
Company, Inc.
Klein, D. R. (2017). Organic chemistry (3rd ed.). John Wiley and Sons, Inc.
Nicholson, J. W. (2006). The chemistry of polymers (3rd ed.). Royal Society of Chemistry.
Smith, J. G. (2011). Organic chemistry (3rd ed.). McGraw-Hill.
Wade, L. G. (2013). Organic chemistry (8th ed.). Pearson Education Inc.

Prepared by: Mark Merrill N. Mesa Reviewed by: Brenda A. Pelagio

Position: Special Science Teacher III Position: Special Science Teacher IV
Campus: PSHS-CVC Campus: PSHS-CLC

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