Chapter 1.

Introduction to Chain Molecules

1.1 Overview of the Course

What Is A Polymer?
Polymer (Greek: poly & meros): “many” & “parts”

Intramolecular forces: covalent bonds

Intermolecular forces: hydrogen bonds;

dipole-dipole interactions;
London forces.

Feature: High molecular weight.

How Big Is Big?

Molecular weight in the range 103-107 g⋅mol-1 or more

Another term: Macromolecules

 2

Applications of polymers:
• Leading today’s materials world; replacing metals, glass, wools
in numerous applications;
• Extensive commodity applications in every aspect and industry
with everal hundred pounds of polymers produced each year for
each person in US;
• Speciality high-performance applications: bullet-proof armors,
fire-retardant vests, artificial hip joints, ultra-strong fibers.
• Play a central role in many emerging technologies: plastics
electronics, gene therapy, drug delivery, biomaterials, optical
data storage, fuel cells, etc.

Food course

French fries -- starch

Cheese -- protein

Fast food boxes --polystyrene foam Trays --- polyethylene

Napkins -- cellulose
 3

Clothings (fibre)

Acrylics (polyacrylonitrile/ rayon) Nylon

(Spandex---polyurethane)

Spandex---polyurethane Polyester

Shoes

Running shoe—nylon PVC

Sole --- SBS rubber
 4

Insole padding -- polyurethane

Shoe laces -- nylon

Polyethylene Duck shoes -- polyisoprene

Sporting Stuffs

Inner liner—polyisobutylene Thread—nylon, polyesters

Cover - Surlyn
Frame -- carbon fiber (thermoplastic elastomer)
Strings-- nylon.

Outer parts of roller blades -- polyethylene

 5

Auto parts

Body parts -- acrylonitrile-butadiene-

styrene plastic (ABS)

Tread -- styrene/ butadiene (SBR) polyisoprene

Sidewalls – polyisoprene rubber
Inner liner—polyisobutylene rubber
Reinforced -- Kevlar

Polybutadiene Body filler -- polyester

Polyethylene Nylon
 6

Paints and decoration

Nylon.
(stain resistant treated with
polytetrafluoroethylene)

Padding -- polyurethane

PVC plastic Polypropylene

(kitchens and bathroom) (indoor/outdoor)

Formica
(Melamine-formaldehyde resin)

Corian and Gibraltar

(heat resistance—
poly(methyl methacrylayte)

Walls: acrylic paints (poly(methyl methacrylate), poly(vinyl acetate) copolymers)

Polymer properties

Advantages:
1. Corrosion and chemical resistance
2. Good thermal and electrical insulating properties
3. May be made isotropic or anisotropic
4. Good strength/ mass ratio
5. Light weight
6. Ease of processing
7. Available in a variety of forms
 7

8. Capable of being formed or made flexible

9. Available as transparent, translucent, or opaque
10. Available in wide range of colors

Disadvantages:
1. Dimensional instability
2. Limited useful thermal range
3. Fragility (may break, crack, or scratch easily)
4. Flammability
5. Absorb moisture
6. Non-degradability
7. Subject to attack by chemicals (deteriorate)
8. Odors or chemical fumes in processing
9. Difficulty or repair (thermosets)
10. Cost (vary by family)

Identification Methods and Applications

• Trade name

• Appearance
Thermoplastic: powder, granular, pellet
Thermosetting: powder, preform, resin
Thermoplastic: extruded, injection-
formed, calendered, blow-molded,
vacuum-molded;
Themosetting: compression-molded,
transfer molded, cast, laminated.

Plastics Appearance Applications

Polyolefins Waxy feel, tough, soft, Carpeting, chair, dish,
translucent. medical syringes,
containers
Vinyls Tough, some flexible, Ball, doll, floor,
transparent rainwear, wall tile,
wallpaper, garden hose
polystyrene Brittle, white bend marks, Bottle cap, dish, blister
metal-like ring when package, lenses,
 8

struck, transparent transparent display box

Acrylics Brittle, hard, transparent Model, glazing, wax
ABS Styrene-like, tough, Appliance, tool
transparent housing, luggage,
sporting goods,
instrument panel
acetal Tough, hard, waxy feel, Aerosol stem valve,
translucent lighter, zipper,
plumbing, belt
Alkyds Hard, tough, brittle, Electrical, paint
opaque
Allyl Hard, filled, reinforced Electrical, sealer
Aminos Hard, brittle, opaque Knob, cap, handle
Cellulosics Tough, transparent Explosive, packing, toy
pharmaceutical, handle
Epoxies Hard, filled, reinforced, Adhesive, casting,
transparent finish
fluoroplastics Tough, waxy feel, Antistick coating,
translucent bearing, gasket, seal,
electrical
Phenolics Hard, brittle, reinforced, Adhesive, ball, handle
transparent
Polyamide Tough, waxy feel, Comb, door catcher,
translucent gear
polyarylsulfone Tough, stiff, opaque, Aerospace, industry
carbonate like
polycarbonate Styrene-like, tough, Beverage dispenser,
translucent film, lenses, light
fixture, windshield,
appliance
aromatic Stiff, tough, opaque Coating, insulation,
polyester transistor
unsaturated Hard, brittle, filled, Furniture, radar dome,
polyester transparent tank, sport equipment
polysulfone Polycarbonate-like, rigid Aerospace, distributor,
cap, hospital
equipment
Silicone Tough, hard, filled, Artificial organ, grease,
reinforced ink, mold, polish
Urethane Tough casting, foam, Bumper, cushion, tire,
 9

flexible, opaque elastic thread, sponge

• Effect of heat

Thermoplastic: hot tip of soldering gun sinks into it

Thermosetting: stays hard and merely chars.

Polytetrafluoroethylene 327 Ethyl cellulose 135

Polyimide 300 Polyallomer 120
Fluoronated ethylene 275 Ionomer 110
propylene
Polyamide 6,6 265 Polyethylene 110
Cellulose acetate 230 Acrylic 105
Polychlorotrifluoro- 220 Polyvinyl alcohol 105
ethylene
Polyvinylidene chloride 210 Polyphenylene oxide 105
Polysulfone 200 Polystyrene 100
Acetal 181 ABS 100
Polypropylene 176 Phenoxy 93
Polycarbonate 150 PVC 75
Cellulose acetate 140 Polyvinyl acetate 60
butyrate

• Effect of solvent
Polymer Acetone Benzene Furfuryl Toluene
alcohol
ABS l p l s
Acrylic s s p s
Cellulose s p s p
acetate
Cellulose s p s p
acetate
butyrate
Fluorocarbon l l l l
Polyamide l l l l
PC l l l l
PE l l l l
PP l l l l
PS s s p s
Vinyl acetate s s l s
Vinyl chloride s l l P
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• Relative density
Fluoroplastics 2.12-2.2 Casein 1.35
Epoxies 1.11-1.8 Chlorinated 1.4
polyester
Aminos 1.47-1.65 Silicone 1.05-1.23
Phenolic 1.26-1.55 Urethane 1.15-1.2
Polycarbonate 1.2-1.52 Polysulfone 1.24
Vinyls 1.2-1.55 Polyamide 1.09-1.14
Polyester 1.01-1.46 Phenylene oxide 1.06-1.1
Acetal 1.4-1.45 PS 0.98-1.1
Allyl 1.3-1.4 Polyolefins 0.91-0.97
Cellulosics 1.15-1.4 Ionomers 0.93-0.95
ABS 1.02-1.25 Acrylic 1.17-1.2

• Mechanical properties
Compressible strength (ASTM D- Force per unit area (KPa,
695) MPa)
To rupture or
crush material
Tensile strength (ASTM D-638) To pull until break
Modulus of elasticity (tensile Stress/ strain
modulus)
Impact strength (toughness) Energy required to break
sample
Falling mass test Container, dinnerware,
helmet, firm
Pendulum test (ASTM D256/ D618) Charpy, Izod
Flexural strength (ASTM D-790, Stress to break sample via
D747) bending
Shear strength Stress needed to produce
fracture by shearing action
Fatigue & flexing(ASTM D-430/ Number of cycles through
D813) which sample can be
deformed before fracture
Hardness(ASTM D-785, D1706, D- Resistance to penetration or
618) indentation by another
body (or to compression,
indentation, abrasion and
scratching)
Brittleness (ASTM D-746) Temperature at which 50% of
sample fall, tested with
impact apparatus
(crystallinity increase
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brittleness at low
temperature)
Friction PE, teflon, polyacetal,
polyamide have low
coefficient of friction

• Physical properties

Relative density, viscosity, specific volume,

dimensional stability (due to flow and creep, swelling
and shrinking, internal stress, temperature change,
weathering and aging)

• Thermal properties

Thermal conductivity, specific heat, coefficient of

thermal expansion, heat deflection, resistance to
cold, burning rate, flammability, melt index, glass
transition point, softening point

• Optical properties

Gloss, luster, haze, transparency, color, clarity, refractive

index

Light transmission %:
PMMA 94; PS, PC 90; cellulose acetate 87; polyvinyl
chloride acetate 83

• Electrical properties

Arc resistance, insulation resistance, dielectric strength,

dielectric constant, dissipation factor.

Ingredients of Polymer Products

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reasons: improve processability, reduce cost, reduce

shrinkage, permit higher curing temperature
by diluting reactive material, improve surface
finish, change thermal properties (expansion
coefficient, flammability, conductivity)

Improve electrical properties, prevent

degradation, provide color, improve
mechanical properties, low friction.

resins
alloy: two or more different polymers are
physically mixed during melt
blend modified by addition of elastomer

additives
antioxidant PE, PP needed most
(stabilizer)
antiozonant
UV olefins, PS, PVC, ABS, polyester,
polyurethane, PMMA
antistatic on surface, absorb moisture, e.g.
amine, quaternary ammonium
compound, organic phosphate,
polyethylene glycol ester
colorant dye, organic pigment, inorganic
pigment, special-effect pigment
dye (coal-tar chemical): color
material by forming chemical
linkage with molecule;
pigment: mix with material
luminescence fluorescence – emit only when
electrons are being excited, made
from sulfides of zinc, calcium,
magnesium;
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phosphorescence – process after-

glow, made from calcium sulfide or
strontium sulfide

coupling agent surface treatment to improve

interfacial bond between matrix,
reinforcement, filler, laminate, e.g.
silane, titanate.

curing agent cause crosslinking, e.g. peroxide

(hardener)

flame combination of bromine,

retardant chlorine, antimony, boron,
phosphorus, emit fire-extinguishing
gas, form insulation barrier

foaming foaming, blowing, frothed,

/blowing cellular, bubble, azo-
agent dicarbonamide to HDPE, PP. ABS,
PS, PVC, EVA

heat retard decomposition, e.g.

stabilizer calcium/zinc in PVC package,
organophosphite in PVC, HDPE,
PP, ABS, PS

impact elastomer, e.g. PVC plus ABS,

modifier CPE, EVA

lubricant wax as montan, carnauba, paraffin,

stearic acid, metallic soap as
stearates of lead, cadmium,
barium, calcium, zinc
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plasticizer improve ability to flow or become

fluid under force, e.g. phthalates,
adipates.

preservative kill microorganisms

processing antiblock using solvent

Objective of the course:

How to produce polymers
How to control polymer structure
How to characterize polymers
What material properties of polymers
What’s new in the field

1.2 Polymer History

• Prehistoric activities

Making wine, vinegar, pottery, glass, metallurgy, dyeing

art of food preparation, caulking of ships, spinning,
weaving of textiles, tanning of hides, painting,
waterproofing with natural rubber

• Development in pre-twentieth century

Cachuchu (“the wood that weeps”) was used for

recreating, religious rites and waterproofing by American
Indians long before Columbus landed in West Indies
1492;

Joseph Priestly used cachuchu for pencil mark eraser,

coined rubber for Hevea braziliensis 1770;
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Michael Faraday showed rubber have C5H8 in 1826;

John Jacob Berzelius coined “polymer” in 1833;

Charies Goodyear discovered vulcanization process in

1839;

Henry Victor Regnault, E. Simon described polymers of

vinyl chloride, vinylidene chloride, styrene in 1838 and
1839;

In 1839, Charies Goodyear purchased patent, accidently

allowed patented mixture remain overnight on hot stove,
and obtained more versatile product “vulcanite”, but did
not patented until 1843.

John Wesley Hyatt patented molding mixtures of

Pyroxiline and camphor under heat and pressure 1869
and 1870’s; Isiah Smith Hyatt (John’s brother) coined
“Celluloid” and registered trademark in US. Celluloid
originally for biliard balls, later for dentures, shirt fronts,
photo film, hairpins, combs, < 500 tons annual in 19th
century;

Natural rubber chlorinated by G.A. Englehard and H.H.

Day in 1859, hydrochlorinated in 1881, isomerized by
Leonhardi in 1881, commercialized early part of 20th
century;

PVC described by Regnault in 1838, by Meyer 1866, by

Baumann (consider PVC as isomer of VCM) 1872,
commercialized 1930’s;

Polymerization of styrene and acrylic acid observed 1872

commercialized early part of 20th century;
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Kelule suggested protein, starch, cellulose consisted of

very long chains;

Emil Fisher reported unusually high MW for natural

polymer

All progress in polymer science and technology was made

by small number of artisans and entrepreneurs, and
smaller number of scientists. “Golden age” started when
concept of macromolecule by H. Staudinger was accepted
in 1920’s.

• Staudinger’s struggle for macromolecular concept

What to learn:
polymer to macromolecule: art to science;
a scientist’s determination to pursue the truth;
possible difficulties a scientist may face; basic
skill in scientific reasoning;
some historical major events during the turning
point:

in 1920, Hermann Staudinger at 39 decided to

devote his efforts to the so-called high molecular
compounds (cannot be purified by distillation or
crystallization) referred as “grease chemistry”;
strong opposition to high molecular concept, e.g.
an admonition by H. Wieland: “Drop the idea of
large molecules, organic molecules with a
molecular weight higher than 5000 do not exist.
Purify your rubber !then it will crystallize.”

in those days each of the important natural

products, such as wood, cellulose, starch, wool,
leather, and rubber, considered a large separate
discipline and empirically investigated; each
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discipline was a world by itself, just like Jupiter and

Saturn before Copernicus.

on March 13, 1920, HS published 12 pages

“Ueber Polymerization”. He reviewed 60 papers
and proposed to use “polymerization” only where
individual small units are combined to the larger
ones by “normal covalent bonds”; he built a new
unified principle: long chain structure. 1920-1926,
he added more than 25 articles. 1922, he coined
“macromolecule”.

HS was attacked by a number of prestigious

scientists. His most important opponents were the
then leading organic chemists as Herzog, Karrer,
Pringsheim, Hess, Bergmann, and Pummerer who
championed a notion that cellulose, starch,
protein, and rubber are aggregated of small
molecular species exhibiting “colloid behavior”.
HS resolved difference in opinion by new
experiments carried out with methods of classical
organic chemistry. For example, he selected NR
because C. Harries and R. Pummerer has
postulated that rubber consisted of small cyclic
isoprene units which were associated through
“partial valencies” emerging from the double bond
of the rubber. HS tried to remove the double
bonds by hydrogenation and found that the
hydrogenated rubber was very similar to the
original sample, not as expected to be a lube oil.

HS presented the results at 3 international

meetings: Innsbruck 1924, Zurich 1925, and
Duesseldorf 1926, but all met lively opposition
from exponents of aggregation concept who
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concluded that it could just as well be the result of

colloidal aggregation, and leading
crystallographers who did not believe that a
molecule can be larger than crystallographic basic
cell.

HS directed his work to meet the arguments put

up against him, X-ray studies of
polyoxymethylenes between 1926 and 1929
showed conclusively that the chain molecules of
these polymers were passing through many
crystallographic basic cells and clarified the
relationship between molecular weight and X-ray
data. Extensive viscosity measurements,
ultracentrifuge studies, and most of all synthetic
work of HS summarized his struggle on the
concept of macromolecule in 1932.

HS was awarded Nobel Prize in Chemistry in

1953, for his discoveries in the field of
macromolecular chemistry, and passed in 1965.
• Other Nobel Winners
1963, Karl Ziegler and Giulio Natta awarded for
their discoveries in the field of the chemistry and
technology of high polymers;
1974, Paul Flory awarded for his fundamental
achievements, both theoretical and experimental,
in the physical chemistry of the macromolecules;
1991, deGennes awarded for his fundamental
contributions in the fields of liquid crystal and
polymer physics.
2000, Alan J. Heeger, Alan G. Macdiarmid, and H.
Shirakawa awarded for the discovery and
development of conductive polymers.
 19

2005, Yves Chauvin, Robert H. Grubbs, and

Richard R. Schrock awarded for the development
of the metathesis method in organic synthesis.

• Chronological development of commercial polymers

1868 cellulose nitrate eyeglass frame
1909 phenol-formaldehyde telephone handset
1909 cold molded knobs and handles
1919 casein knitting needles
1926 alkyd electrical bases
1926 analine-formaldehyde terminal boards
1927 cellulose acetate toothbrushes
1927 polyvinyl chloride raincoats
1929 ethyl-formaldehyde lighting fixtures
1935 ethyl cellulose flashlight cases
1936 acrylic brush backs
1936 polyvinyl acetate flash bulb lining
1938 cellulose acetate butyrate irrigation pipe
1938 polystyrene or styrene kitchen housewares
1938 nylon (polyamide) gears
1938 polyvinyl acetal safety glass interlayer
1939 polyvinyldene chloride auto seat covers
1939 melamine formaldehyde tableware
1942 polyester boat hulls
1942 polyethylene squeezable bottles
1943 fluorocarbon industrial gaskets
1943 silicone motor insulation
1945 cellulose propionate automatic pens and pencils
1947 epoxy toots and jigs
1948 acrylonitrile-butadiene-styrene luggage
1949 allylic electrical connectors
1954 polyurethane or urethane foam cushions
1956 acetal automotive parts
1957 polypropylene safety helmets
1957 polycarbonate appliance parts
1959 chlorinated polyether valves and fittings ·
1962 phenoxy bottles
1962 polyallomer typewriter cases
1964 ionomer skin packages
 20

1964 plyphenylene oxide battery cases

1964 polyimide bearings
1964 ethylene-vinyl acetate heavy-gauge flexible
1965 parylene sheeting
1965 polysulfone insulating coatings
1965 polymethylpentene electrical and electronic parts
1970 poly(amide-imide) food bags
1970 thermoplastic polyester films
1972 thermoplastic polyimide electrical and electronic parts
1972 perfluoroalkoxy valve seats
1972 polyaryl ether coatings
1973 polyethersulfone recreation helmets
1974 aromatic polyesters oven windows
1974 polybutylene circuit boards
1975 nitrile barrier resins pipes
1976 polyphenylsulfone packaging
1978 bismaleimide aerospace components
1982 polyetherimide circuit boards
1983 polyetheretherketone ovenable containers
1983 interpenetrating network (IPN) wire coating
1983 polyarylsufone shower stalls
1984 polyimidesufone lamp housings
1985 polyketone convey links
1985 polyether sulfonamide automotive engine parts
1985 liquid-crystal polymers cams; electronic components

1.3 Classification of Polymers

1. Source
Natural: amber, asphalt, copal, lignin, shellac, tar
Modified natural: casein, cellulose, gelatin, protein, rubber
Synthetic: agricultural products, coal, natural gas, petroleum

Rubber: made from a milky juice called latex

Natural rubber: from hevea tree.

2. Light penetration:
 21

Opaque, transparent, translucent, luminescent

3. Heat reaction (processing characteristics)

Thermoplastics acrylics, cellulosics, polyamide, polystyrene,

polyethylene, fluoroplastics, polyvinyls,
polycarbonate, polysulfone.

Thermosetting aminos, casein, epoxies, phenolics,

polyesters, silicones, polyurathanes.

4. Polymerization reaction (method of formation)

Polyaddition (chain-growth) free-radical

ionic (anionic, cationic)
Ziegler-Natta, metallocene
Polycondensation (step-growth)

5. Molecular structure:
Linear, branched, crosslinked, star, comb, hyperbranched,
dendrimer, cycle
Homopolymer, copolymer

6. Crystal structure
Crystalline, amorphous
7. Mechanical behavior
Plastic, elastomer, fibre

8. Polymerization processes:
Bulk, solution, precipitation, suspension, emulsion, gas phase
Chloroprene (CR) emulsion
 22

LDPE bulk
HDPE solution, gas phase
Polyacetals solution
Polyamide (PA) bulk, suspension
Polycarbonate (PC) bulk
Polyethylene terephthalate (PET) bulk
Polyisoprene (IR) solution
PMMA bulk,suspension, solution
Polypropylene (PP) solution, gas phase
Polystyrene (PS) emulsion, suspension,
bulk, solution
Polysulfides suspension
Polytetrafluoroethylene suspension
Polyvinyl chloride (PVC) emulsion, suspension
Polyvinyl acetate (PVA) emulsion
SBR emulsion

1.3 Addition and condensation polymers

Addition polymers
(1) The repeat unit in the polymer and the monomer has
the same composition, although the bonding is different
in each.
(2) The polymerization mechanism is in the kinetic
category of chain reaction, with either radical or ionic
groups responsible for propagating the chain reaction.
(3) The product molecules often have an all-carbon chain
backbone, with pendant substituent group.

Polymerization mechanism: chain initiation, propagation,

termination.
23
 24

Condensation polymers
(1) The polymer repeat unit arises from reacting two
different functional groups usually on different
monomers. The repeat unit is different from either
monomer. In addition, small molecules are often
eliminated during the condensation reaction.
(2) The polymerization reactions occur in steps.
(3) The product molecules have the functional groups
formed by the condensation reactions interspersed
regularly along polymer backbone.
−C−C−Y−C−C−Y−
 25

1.4 Linear and Branched Polymers, Homopolymers,

and Copolymers

1.4.1 Branched structures

Polymers of different architectures:

• Linear polymers,
• Branched polymers: star polymers, comb polymers,
hyperbranched polymers, dendrimers
• Cross-linked polymers
• Cyclic polymers

Branches: additional polymer chains issuing from the backbone of

a linear molecule.

Small substituent groups on the repeat units are generally not

considered branches; or specified as “short-chain branches”.

1.4.2 Copolymers
 26

It’s not necessary to have all repeat units to be the same in a

polymer.

Homopolymers: polymers containing a single kind of repeat unit.

Copolymers: polymers containing more than one kind of repeat

unit.

Terpolymers: containing three kinds of repeat unit.

Multicomponent polymers: containing more than three kinds of

repeat unit.

These definitions are based on the repeat unit, not the monomer.

To quantitatively describe the copolymers, relative amounts of

different kinds of repeat units must be specified.

Empirical formula of a copolymer: AxBy

x and y: the relative numbers of repeat units A and B.

Distribution of different kinds of repeat units:

• Random (or statistical): called poly(A-ran-B)
-AAABABAABBABBB-
• Alternating: called poly(A-alt-B)
-ABABABABABABAB-
• Block:
-AAAAAAAAAA-BBBBBBBB-AAAAAAA-
Three blocks: poly(A-block-B-block-A)
• Graft: with different repeat units occurring in the branches
and the backbone

Sequence determination.
 27

1.5 Molecular Weights and Molecular Weight Averages

1.5.1 Some terms

Molecular weight (molar mass)

Polymers: average molecular weights

Repeat units:
• Structural elements covalently bonded together to form a
polymer.
• One or two types in most polymers.
• They are the parts of monomers
• molecular weight of repeat unit designated as M0

Degree of polymerization (N): the number of repeat units in a

molecule. N = M/M0

In addition polymers:
• the molecular weight of monomer and repeat unit is identical

In condensation polymers:
• small molecules are eliminated in the condensation reaction
• molecular weight of the monomer and the repeat unit are
different.
• for polyesters from diol and diacid
M M
N= =
M 0 M A + M B − 2M H 2O

The effect of end group on the calcaulation of polymer molecular

weight.

1.5.2 Number-, Weight-, and z-Average Molecular

Weight
 28

Polymers show polydispersity in their molecular weight or degree

of polymerization due to the statistic nature of the polymerization.

Assume a polymer containing many molecules with different

degrees of polymerization.

Define a molecule with degree of polymerization i as an i-mer with

molecular weight of Mi = iM0.

The number of i-mers is ni moles.

The total number of molecules in the polymer is: ∑i ni

The number fraction or mole fraction of i-mer is:

ni
xi =
∑ni i

The weight fraction of i-mer is:

ini
wi =
∑i ini

Number-average molecular weight (Mn) is defined as:

M n = ∑ xi M i =
∑nM
i i i
= Mo
∑ in i i

i ∑n i i ∑n i i

Weight-average molecular weight (Mw) is defined as:

2 2

M w = ∑ wi M i =
∑ in M
i i i
=
∑nM
i i i
= Mo
∑i n
i i

i ∑ in i i ∑nM i i i ∑ in i i

z-average molecular weight is defined as

Mz = Mo
∑ i n (not directly related to a fraction)
i
3
i

∑i ni
2
i

1.5.3 Polydispersity Index an Standard Deviation

 29

To describe the breath of molecular weight distribution,

polydispersity index (PDI) is defined as:

PDI = Mw/Mn

PDI is always greather than 1 (when PDI =1, monodisperse)

Typical polymerization gives PDI about 2

Industrial processes: PDI can be as large as 10 or more.

When PDI: < 1.5, narrow distrubition; > 2, broad

To characterize a distribution: a mean and a standard deviation

In MWD, the mean is Mn,

1/ 2
⎡ M ⎤
The standard deviation is: σ = M n ⎢ w − 1⎥
⎣ M n ⎦

Example 1.5

The distribution functions: xi, wi wi = xi M i / M n

A particular mathematical function: Schulz-Zimm distribution

z z +1 M iz −1 zM i
xi = P ( M i ) = z
exp(− )
Γ( z + 1) M n Mn

z z +1 M iz zM i
wi = z +1
exp(− )
Γ( z + 1) M n Mn
 30

M w z +1
=
Mn z

1.5.4 Measurement of molecular weight

 31

Measurement of molecular weight is the most important step in

characterizing a polymer sample.

A variety of experimental techniques are available.

1.6 Polymer Nomenclature

Various nomenclature systems existing:

• Systematic IUPAC system (based on the structure of
monomer or repeat unit,
• Semisystematic trivial names
• Trade names for commercially important synthetic polymers;
• Biological polymers named in terms of their function,
separation, or characterization

The following nomenclature is used in this book:

 32

Polymers formed from a single monomer:

• add prefix poly to the name of the monomer,
• the monomer is named following IUPAC nomenclature for
organic chemistry or with a common name, (CH2-CHCl)n is
called poly(1-chloroethylene) or poly(vinyl chloride)
• parentheses may or may not be used, polyvinyl chloride
• some polymers are named as being drived from hypothetical
monomers, poly(vinyl alcohol) or polyvinyl alcohol, or poly(1-
hydroxyethylene), the monomer vinyl alcohol is hypothetical.

Polymers by condensation polymerization of two different

monomers:
• Named by applying the same rules to the repeat unit.
e.g., polyester from ethylene glycol and terephthalic acid
poly(oxyethylene oxyterphthaloyl) IUPAC system
poly(ethylene terephthalate) more commonly
polyamides, poly(hexamethylene sebacamide) nylon-6,10
poly(hexamethylene adipamide) nylon-6,6

Some commercial important cross-linked polymers:

• Called resins, and named by specifying the monomers for
their production.
e.g., phenol-formaldehyde, urea-formaldehyde resins

1.7 Structural Isomerism

Positional isomerism

Stero Isomerism

Geometrical isomerism
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34