Synthetic and Biological Polymers

Polymers: Macromolecules formed by the covalent

attachment of a set of small molecules termed monomers.

Polymers are classified as:

(1) Man-made or synthetic polymers that are
synthesized in the laboratory;
(2) Biological polymer that are found in nature.

Synthetic polymers: nylon, poly-ethylene, poly-styrene

Biological polymers: DNA, proteins, carbohydrates

1
Hydrocarbons
ex: Alkanes
 1 – Meth-
 2 – Eth-
 3 – Prop-
 4 – But-
 5 – Pent-
 6 – Hex-
 7 – Hept-
 8 – Oct-
 9 – Non-
 10 – Dec-
 11 – Undec-
 12 – Dodec-
 Hydrocarbons
at Room Temperature
 Gas  Liquid  Waxy  Plastic
 Methane 20 to 40 40 or more
 Ethane 5 to 19 Carbons Carbons
 Propane Carbons
 Butane
Melting Point
 As the length of hydrocarbons get longer, the
Melting Point grows Higher. Why?

Melting and Boiling Temperatures of Alkanes

1.2

1
Tempurature (˚C)

0.8

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
Number of Carbons
What other material properties
change?
 Viscosity

 Hardness

 Toughness

 Flammability
Bonding

 Covalent

 Ionic (NaCl)

 Polar (H2O)

 Van der Waals

 Methods for making polymers

Addition polymerization and condensation polymerization

Addition polymerization: monomers react to form a

polymer without net loss of atoms.

Most common form: free radical chain reaction of

ethylenes

n monomers one polymer molecule

7
Example of addition polymers

8
Free-Radical AdditionPolymerization of
Ethylene
H2C CH2

200 °C O2
2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
Free-Radical Polymerization of Propene

H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
 ..
RO
.. • Mechanism
H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 Likewise...

•H2C=CHCl polyvinyl chloride

•H2C=CHC6H5 polystyrene

•F2C=CF2 Teflon
Important
constitutions
for synthetic
polymers

19
Supramolecular
structure of
polymers

20
Structural
properties of
linear
polymers:
conformationa
l flexibility
and strength

21
Molecular Structure
of Polymers
 Linear
 High Density Polyethylene (HDPE), PVC, Nylon,
Cotton
 Branched
 Low Density
Polyethylene (LDPE)
 Cross-linked
 Rubber
 Network
 Kevlar, Epoxy
Chain Length: 1000 - 2000

Low-Density Polyethylene (LDPE)

 Chain Length: 4,000 – 5,000

PVC – (polyvinyl chloride)

More Polar  Stronger Bonding

Chain Length: 10,000 – 100,000

High-Density Polyethylene (HDPE)

Chain Length: 2-6 million

Ultra-high-molecular-weight
polyethylene (UHMWPE)
Joint
Replacement

Helmet

Gears
Rubber Tree

 Sap:
 Sticky
 Viscous
 Gooey

 Goodyear
 Experiment
 Luck
 Profit ($0)
Vulcanization
 Condensation polymerization

Condensation polymerization: the polymer grows from

monomers by splitting off a small molecule such as
water or carbon dioxide.

Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

29
Chain Length: 4,000 – 8,000

Polyethylene Terephthalate (PETE)

“Polyester”

Ester
 Kevlar

Strong Network of Covalent Bonds

And Polar Hydrogen Bonds
Rembember from GChem?

Nylon is a condensation polymer

made of the monomers adipic acid
and hexamethylene diamine.

O OH
O

OH
Q uickTim e™ and a
Phot o - JPEG decom pr essor
ar e needed t o see t his pict ur e.

They're nylons, Benjamin.

adipic acid
+
NH2
H2N

hexamethylene diamine

nylon
32
Nylon
 Hydrogen bonds between chains

Supramolecular
Structure of
nylon

Intermolecular
hydrogen bonds
give nylon
enormous tensile
strength

34
 Biopolymers

Nucleic acid polymers (DNA, RNA)

Amino acids polymers (Proteins)

Sugar polymers (Carbohydrates)

Genetic information for the cell: DNA

Structural strength and catalysis: Proteins

Energy source: Carbohydrates

35
 Proteins: amino acid monomers

The basic structure of an amino acid monomer

HO NH2
H
O R

The difference between amino acids is the R group

 Cotton

Long Strands of Cellulose

+ Hydrogen Bonds

Cellulose is the most common organic material on earth!

It is also a primary constituent of wood and paper.
Polymers in Starch
Biology
DNA

Sugar Proteins
39
 Proteins: condensation polymers

Formed by condensation polymerization of amino acids

Monomers: 20 essential amino acids

NH2 General structure of an amino acid
H R
CO2H R is the only variable group

Glycine (R = H) + Glycine First step toward poly(glycine)

40
Representation of the
constitution of a protein

41
Three D representation of the structure of a protein

42
DNA
 Thymine (T)
The monomers:

Adenine (A)
Cytosine (C)

Guanine (G)

Phosphate-
Sugar (backbone) of
DNA
44
Phosphate-
sugar
backbone
holds the DNA
macromolecule
together

45
One strand
unwinds to
duplicate its
complement via a
polymerization of
the monomers
C, G, A and T

46
Carbohydrates
48
Endless Possibilities

 New
Functional
Groups

 Different
Polymer
Backbones
Conclusions:
 Polymers make up all sorts of materials that
are all around us!
 They can have a huge range or material
properties based on their:
 Functional Groups
 Structure
 Backbone
 Keep thinking about how chemical
interactions on the nano-scale correspond to
material properties on the macro-scale
Links
 http://en.wikipedia.org/wiki/Plastic_recycling
 http://en.wikipedia.org/wiki/Alkane
 http://en.wikipedia.org/wiki/Higher_alkanes
 http://en.wikipedia.org/wiki/Ultra-high-molecular-weight_polyethylene
 http://en.wikipedia.org/wiki/Polycondensation
 http://www.chemistryland.com/ElementarySchool/BuildingBlocks/BuildingOrg
anic.htm
 http://www.ndt-
ed.org/EducationResources/CommunityCollege/Materials/Structure/polymer.
htm
 http://www.bbc.co.uk/schools/gcsebitesize/science/21c/materials/molecstru
ctpropertiesrev3.shtml
 http://en.wikipedia.org/wiki/Van_der_Waals_force
 http://en.wikipedia.org/wiki/Vulcanization
 http://www.scribd.com/doc/26766586/08-Polymers-Why-is-Rubber-Elastic
 http://www.ndt-
ed.org/EducationResources/CommunityCollege/Materials/Structure/polymer.
htm