POLYMER SCIENCE AND TECHNOLOGY b.

Intermolecular – forces between two chains,

I. Introduction and Basic Concepts
Polymers- long chain molecules,
Polymer properties- cheap, corrosion resistant,
lightweight, good formability
By Origin:
a. synthetic organic polymers – mostly from
petrochemicals
b. biopolymers – proteins, natural rubber
c. semi-synthetic – chemically modified
biopolymers, easy to degrade
d. inorganic- carbon replaced by Si
Important notes:
 Elastomers are polymers that are
capable of high extension under
ambient ( ex. Rubber, tire, nitrile butyl
rubber)
 Nylon and polyester are example of
polymers that are suitable into long
fibers
 Plastics, another kind of synthetic
polymer, often with additives and fillers
 Monomer – repeating unit
 N, degree of polymerization (DP) - # o
repeating units
 Oligomer – fewer than 10 repeating
units
 Homopolymer – one king of repeating
unit
 Copolymer – more than one kind of
repeating units
 Terpolymer- three different repeating
units
 MW(poly) = MW(rep) X DP
Molecular forces:
a. Intramolecular – forces between atoms in
one chain (impt. for amorphous)
Primary bonding: (intra)
Ionic bond
Covalent bond*
Coordinate bond
Metallic bond
(impt. for crystalline)
Secondary bonding: (inter)
vdW
Dipole forces
H-bonding*
Induction forces
c. Entanglements (impt. for amorphous)
Functionality:
 Number of reactive groups, number of
reactive sites
 Basic functionality required is two
bonding sites (linear chain)
 Higher functionality -> crosslink or
branched
II. Polymer Nomenclature
A. Common Names
- some are named from the place of origin,
some are named from the discoverer, some are
named after the number of carbons
B. Source-based Names
-from the name of the reactant monomer + the
word ‘poly’
-copolymer: poly(A-co-B), types: block,
alternating, graft, and random
(ex. A-block-B-block-C)
C. Structure-based Names
-IUPAC system
-Linkage-based names
D. Chemical abstracts-based polymer
nomenclature
-IUPAC and CAS: based on structural repeating
unit, IUPAC-poly(constitutional repeat unit),
CAS-poly(structural repeating unit)
 Seniority: heterocylic rings>
greatest # of most preferred acyclic
heteroatoms>
carbocyclic rings>
greatest # of multiple bonds >
lowest locant>
only C chains
O>S>Se>Te>N>P>As>Sb>Bi>Si>Ge>Sn>Pb>B>Hg
E. Trade Names, Brand Names and Abv.
III. Polymer Classification B. Physical Properties (thermal response)
A. Origin  Thermoplastics
Natural -heat softened
Semi-synthetic -no crosslinks
Synthetic -weak attractive forces
B. Physical Properties (thermal response)
Thermoplastics  Thermosets
Thermosets -chains are chemically linked by
C. Polymerization Mechanism or Mode of covalent bonds
Formation -crosslinked networls resist heat , creep
Addition and solvent attack
Condensation
D. Polymer Structure C. Polymerization Mechanism or Mode of
Based on backbone Formation
Homochain  Addition
Heterochain -from unsaturated monomers (double
Arrangement of monomer bond) or closed rings (ring-opening
Homopolymer polymerization)
Copolymer (random, alternating, block, -most are chain growth
graft)  Condensation
Type of Molecular structure/ Line structure -from random reaction of two
Linear –two ends molecules having complementary
Branched – have side chains functional end units
Cross-linked - networked -with liberation of a small molecule in
Type of functional group the form of a gas, water or salt
Alcohol, ester, etc. -most are step-growth
E. Tacticity
Isotactic D. Polymer Structure
Syndiotactic Based on backbone
Atactic  Homochain – one atom
F. Crystallinity  Heterochain – more than one atom
Amorphous (non-crystalline) grouped according to the types of
Semi- crystalline atoms and chemical groups
Crystalline
G. Application and Physical properties Arrangement of monomer
Rubbers/Elastomers  Homopolymer
Plastics  Copolymer (random, alternating, block,
Fibers graft)
Paint and Adhesives *The actual squence of monomer units
A. Origin is determined by their relative
 Natural – available in nature reactivities
 Semi-synthetic- chemically modified *Long block monomers , AB-block
natural polymers (hydrogenated, copolymers ot triblock copolymers
halogenated) *Graft copolymers can be prepared by
 Synthetic – man-made poymerizing a monomer in a presence
of a fully formed polymer or another
monomer.
 Type of Molecular structure/ Line
structure
 Linear – with two ends
-soluble, fusible
 Branched – have side chains
-side chains are results of
uncontrolled side rxns or by
design
-more soluble, fusible than
linear
 Cross-linked – networked
-insoluble, infusible
-shows order of swelling
Type of functional group
 Polyester
PET (or PETE) – thermoplastic, used in
synthetic fibers containers,
thermoforming apps, often in
combination with glass fiber
 Polyolefin
From simple olefin (alkene), polyalkene,
petrochemical industry, ex.
polypropylene
 Polyamide
Amides joined by peptide bonds,
commonly used in textiles, carpet,
sportswear durable and strong
 Polyether
 Polyurethane
Widely used in high resiliency flexible
foam seating, rigid foam insulation
panels, microcellular foam seals and
gaskets, high perormance adhesivesm
surface coatings
 Polyacrylic
E. Tacticity
-relative streochemistry (configuration, diff
from conformation)
-effect on physical properties
-regularity of macromolecule structure affects
the degree of crystallinity
-head to head, head to tail and random
Head to tail configuration:
 Isotactic – R on the same side of the
planar, (stereoregular)
 Syndiotactic – R on alternate sides of
the planar, (stereoregular)
 Atactic – R are randomly distributed
*stereoregular- high strength and stiffness,
heat resistant, low solubility, high density
F. Crystallinity
 Amorphous (non-crystalline) – lack of
positional order on the molecular scale
 Semi- crystalline - both
 Crystalline
*0 to 90% crytallinity
*affected by structure, temperature, MW,
stereochemistry, processing conditions
G. Application and Physical properties
 Rubbers/Elastomers
Long-range elasticity
Rather weak and unstable
Cross-linked (vulcanization)
 Plastics
Usually stronger than rubbers
Some are hard and stiff, some are soft
and flexible
 Fibers
Strongest among the three
Plant or animal origin
High mechanical strength, thermal
insulation, soft, flexible
 Paint and Adhesives
Important notes on Crystallanity:
 Crystalline- stronger but less flexible
 Crystalline polymers, the denser areas
have higher refreactive index thus,
opaque or translucent, isotactic,
syndiotactic
 High-impact polystyrene – individually
amporphous and transparent but
different refractive indexes thus,
appears white and translucent
  Property-structure relationships
Glass Transition T
- Increases w/ bulky pendant
groups
- Decreases w/ additives
Solubility (lower length)
- Increase amorphous
- Low interchain force
- Disorder
- Temp
- Compatible solvent
Crystallinity (high interchain force)
- Regularity, symmetry
- Decrease volume
- Increased stress
- Slow cooling
- Homogeneous lengths
CRYSTALLINITY
-highly stereoregular, little/no
branching
- highly polar, strong dipole-dipole or H-
bonding
METHODS
1. Cooling of molten polymer
2. evaporation of polymer soln’s
3. heating of polymer under vacuum
4. stretching = drawing
Glass Transition (amprophous region) (glassy
state to rubbery state)
-Below Tg – disordered w/ immobile molecules
-Above Tg – disordered w/ portion where
molecules can wiggle around
-Second order transition
Melting ( crystalline region) (solid to melt)
- Below Tm – ordered solid
- Above Tm – disordered melt
- First order transition
Effects of Crystallinity
1. Mechanical Property
Stronger and stifer
2. More Opaque
Scattering of light
3. Higher Density
4. More solvent resistant
GLASS TRANSITION T (Amorphous phase)
1. Heating from low T – increased kinetic energy
of molecules, increase motion only short range
i.e. vibrations, rotation
2. Glass Transition T , Tg– from brittle crytalline
to rubbery
3. At Higher T, Tm – lose elastomeric properties,
flow as liquid
Factors affecting Tg:
-chain interaction -> chain polarity,
dipole force
-MW, low # of chain ends, low free vol.
-flexibility (rigid-> high)
-steric effect - bulky groups – less
freedom
-stiffness
*high volume of pendant – increase
*flexibilty of pendant – decrease (plasticizing)
*length of pendant – increase
(entanglement/side-chain polymerization)
*flexible substituents – increase free vol.
*branching of pendant – increases
*polarity of pendant – increases
*cross-linking – restricts rotational motion
raises Tg
Tg is influenced by 5 factors:
1. free volume
2. attractive forces
3. internal mobility
4 stiffness
5. chain length
POLYMER PROPERTIES
1. Molecular weight
2. Conformation – arrangement of chains in
space
3. Configuration – arrangement of atoms along
the chain
IV. MOLECULAR WEIGHT
1. Number- Average MW
(total mass/ total no. of moles)
2. Weight- Average MW
(/ total W)
Important notes:
 Mn are determined by Raout’s
techniques and dependent on
colligative properties such has
ebulliometry, cryometry, osmometry,
and end-group analysis
 Mw are determined by expermients
and more dependent on the number of
heavier molecules than the ave weight,
affects the bulk properties such as
viscosities and toughness
Polydisperty index = Mw/Mn – measures the
range of molecular sizes or the breadth of the
molecular weight distribution
3. Viscosity Average MW
-bigger molecules makes a more viscous
solution, molecules flow slowly
-bigger hydrodynamic volume, the volume that
the coiled up polymer takes up in a solution
-slows down the solvent molecules by blocking
their motion
V. Fractionation
-targeted manipulation of the MW distribution
of a polymer by separating and grouping short
and/or long chain materual
Three methods (Polymer Fractionation):
1. fractional precipitation
2. elution fractionation
3. gel permeation chromatography
Five methods (MW determination):
1. end-group analysis
2. colligative properties
3. light scattering measurement
4. ultracentrifuge techniques
5. viscosity measurements
Three methods (Polymer Fractionation):
1. fractional precipitation
-Good solvent to produce solution
-Slowly adding non-solvent/precipitant then
filter
-High MW precipitate first
*constant T- adding precipitant
*solvent – slowly decreasing T
2. elution fractionation
-solid polymer then use increasing solvent
power
-Low MW will dissolve first ( collect high MW)
-use thin film polymers to enhance separation
(increase contact area)
3. gel permeation chromatography
-principle of size-exclusion chromatography
(SEC)
-molecular sieving
-using a column filled w/ swollen crosslink
polystyrene gel resulted in voids in the polymer
gel
-High MW pass first
-Low MW stay longer , passes the voids
Five methods (MW determination):
1. end-group analysis
No. of end group = no. of chains (linear)
2. colligative properties
Boiling point, freesing point and osmotic
pressure
3. light scattering measurement
Information about motion
Higher MW scatter light more
4. ultracentrifuge techniques
To determine the sizes and MW of colloidal and
other small particles
Sedimentation coefficients is a function of size,
shape and density
Larger particles will sediment at lower speed
LIMITATIONS: chain not spherical, size of p. and
solvent, complicated and expensive equip.

5. viscosity measurements
Viscosity dependpends on nature of solvent,
type of P, MW of P, solution conc., T
Gives relative MW