1.
Classification of polymers:
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Flowchart of Polymeric Materials
Inorganic :
Clays, Cement, Sands,Glass, Synthetic Fibres
Organic:
Synthetic – Adhesives, Fibres, Coatings, Rubbers
Natural – Polysaccharides, Proteins, Polyisoprene Rubbers
Various Forms of Polymer
Tailoring of Polymers-to alter the properties
Combination of Different Polymers
Polymer Blend
Polymer Architectures
Linear
Branched
Thermosetting
Hydrogel
Crosslinked
Polymer Architectures(Contd.)
Drug delivery Low viscosity high molecular
weight polymer
Star Polymer
Dendrimer
Benefits and applications?
Interpenetrating network
Molecule vs Macromolecule(Polymer)
Polymer- slow and strong
Long time to solubilize
Longer reaction time
Flow Behavior of Polymers
A dissolved polymer increases the viscosity of the solution
Polymer in cosmetic industry:
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Tacticity
H R H R
C=C C C
H H H H
H RH RH R H RH HH R
C C C C C C C C C C C C
H HH HH H H HH RH H
Isotactic Syndiotactic
H RH RH HH RH H
C C C C C C C C C C
H HH H H RH HH R
Most important
Atactic
commercial polymer
Tacticity depends on the specific conditions of
polymerization such as temperature, choice of solvent,
catalyst
EFFECT OF TACTICITY ON GLASS TRANSITION TEMPERATURE (K)
Polymer Tg(atactic) Tg(isotactic) Tg(syndiotactic)
Poly(methyl
281 272 (283) 299
acrylate)
Poly(ethyl
249 253 (248) 263
acrylate)
Poly(methyl
378 319 (317) 433 (432)
methacrylate)
Poly(n-butyl
293 249 (250) 361 (361)
methacrylate)
Poly(isopropyl
267 264 (262) 285 (278)
acrylate)
Poly(methyl α-
416 353 (358) 452 (450)
chloroacrylate)
Poly(isopropyl
363 321 (341) 392 (409)
α-chloroacrylate)
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Crystalline vs Amorphous Polymer
Solid organic compounds consisting of ordinary small
molecules tend to be crystalline, that is, the molecules
pack themselves in regular three-dimensional arrays.
Polymers can be amorphous (totally lacking positional order
on the molecular scale) or semicrystalline (containing both
crystalline and amorphous regions in the same sample). The
semicrystalline case can be pictured according to the
"fringed micelle" model.
"Fringed micelle"
model
Spherulite
Lamella
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A stacked array of lamellar poly(ethylene) single crystals(AFM image)
Crystallinity can be increased by stretching the polymer
Polymers with chemically and geometrically regular structure are
crystalline in nature. Branching and copolymerization of a minor
amount limit the extent of crystallization
Noncrsytalline polymers: polymers with irregular structure,
copolymers with significant amount of two or more different
monomer constituents, polymers with bulky side groups
Billmeyer p261-263, 266-267
Thermal Transition
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For many polymers the transition between the solid and liquid states is rather
diffuse and difficult to pinpoint.
Amorphous polymers are viscous liquids when they are held at temperatures
above their glass transition temperature, Tg.
Below Tg, the material is solid, yet has no long-range molecular order and so
is non-crystalline. In other words, the material is an amorphous solid, or a
glass.
The glass transition temperature is different for each polymer, but many
polymers are above Tg at room temperature.
In many cases the polymers are at least partially crystalline at room
temperature and the temperature at which the crystalline domains melt (Tm) is
above room temperature.
Changes in properties such as specific volume and heat capacity occur as a
polymer undergoes each of the thermal transition
long-range segmental motion: he polymer chain as a whole may not be going
anywhere, segments of the chain can wiggle around, swing to and fro, and turn like a giant corkscrew.
The polymer samples may be thought of as a crowd of people on a dance floor. While each whole body
tends to stay in the same spot, various arms, legs, and whatnot are
Tg is related to intermolecular forces, chain stiffness and symmetry.
Hidrance to free rotation along the polymer chain resulting from the
presence of stiff bonds or bulky side groups increases Tg.
Tg Tm
Temperature
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Tg depends on
Molecular weight- Tg increases with increase in molecular weight
Crosslinking-tg increases
Flexibility-tg decreases
Intermolecular force(IMF)- Tg increases with increase in IMF
Crystallinity- Tg increases with increase in crystallinity
Solubility of Polymers
Polymer dissolves in two stages
Stage 1: Solvent diffuse in polymer network. Forms
swollen gel
Stage 2: If polymer solvent interaction is highly
favorable true solution forms
Depends on
Crystallinity
Molecular weight
Agitation
Temperature
Intermolecular forces Billmeyer: Ch 7
Solubility of Polymers
Polymer does not exist as an extended chain, instead it has a compact
structure. Each repeat unit rotates randomly, the chain continuously
changes direction, turning back on itself many times and form a random coil
In a bad solvent, the coil is collapsed
In a good solvent, the coil is swollen
In a theta solvent, the coil behaves exactly like an ideal random coil
Random coil: The chain has relative freedom of rotation however has
limited confirmations.
r: root mean square end to end distance
N: number of links
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ad/graessley-talk.pdf
Mass of Polymer
Molar mass of polymer = molar mass of repeat unit x n
Degree of Polymerization(n)
The number of monomeric units in a macromolecule (polymer)(DP)
Molecular Weight
Number Average Molecular Weight
N number of molecules with
mass M
Mass Average Molecular Weight
Viscosity Average Molecular Weight
PDI = Mw/Mn
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FyQCjD_1tx4
https://www.youtube.com/watch?v=
prO5gJSprFQ
Now let's calculate the simple average population of the four cities:
Take Memphis. It has a population of 700,000. The total population of our four cities is
723,500. So the fraction of people who live in Memphis is
0.9675, or we might say, 96.75% of the people live in Memphis. Now let's take our fraction,
0.9675, and multiply that by the population of Memphis:
Now let's do the same thing for all the cities, and add up the answers
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D03.htm
Mn
Amount of polymer
Mv
Mw
Molecular weight
Distribution of molecular weight in a typical polymer
Mw is always greater than Mn. The value of Mw is influenced
by presence of high molecular weight species
Polydispersity : Mw/Mn
1 moles of polymer of MW 10,000 and 1mole of polymer of MW
100,000. Find Mn and Mw
Mn = 55,000
Mw = 92,000
1 polymer with weight 10,000
1 polymer with weight 10,500
1 polymer with weight 20,000
Mn = 13,500
Mw = 15,067
A polydispersed sample of polystyrene is prepared by mixing three
monodispersed samples in the following proportions.
1g 10, 000 mol wt
2g 50,000 mol wt
2g 100,000 mol wt
Determine number average and weight average molecular weight.
Mn = (1 x 10,000 + 2 x 50000 + 2 x 100000)/5 = 62000
Mw = 66452
Calculate Mn, Mw and the polydispersity index for a polymer
that contains equimolar amounts of polymer having molecular
weight of 30,000, 60,000, 90,000.
Mn = (30,000 + 60,000 + 90,000)/3 = 6x 104
Mw = ([30,000]2 + [60,000]2 + [90000]2)/(30,000 + 60,000 + 90,000) = 7 x 104
PDI = 1.16
Determination of Molecular Weight
Mn Osmometry
End group titration
Colligative properties
Mv Intrinsic Viscosity
Mw Light Scattering
Small Angle Neutron Scattering
Sedimentation Velocity
Molecular weight distribution
Gel Permeation Chromatography(GPC)
Osmometry
Osmotic Pressure
c concentration
R real gas constant
T temperature
A2, A3 virial expansion coefficients
The above equation is simplified by taking measurements at different concentrations and
then extrapolating to yield:
c
Pressure Pressure
Gauge Gauge
Solvent Solvent Solvent+ Solvent
Polymer
Semipermeable Semipermeable
membrane membrane
Zimm Plot Equation
When = 0
When c~ 0
R Rayleigh ratio
variable , constant c variable c, constant
1/Mw{
Intrinsic Viscosity
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t sol ' n = sol ' n t solvent = solvent
sol ' n solvent
rel = t sol 'n / t solvent
sol 'n − solvent
sp =
solvent
Both hrel and hsp depend on the polymer concentration, so to extract the "intrinsic" properties of the polymer
chain itself, one must extrapolate to zero concentration.
[] = ( /c)c 0
sp
Mark-Houwink Equation
intrinsic viscosity
K a constant
is a scalar which relates to the "stiffness" of the polymer
chains. If in solution, the polymer molecules are rigid rods,
then a=2. On the other extreme, if the polymers are hard
sphere, a=0. If a=1, the polymers are semicoils. In a Flory
theta solvent, a=0.5, and in a thermodynamically good
solvent a=0.8.
K = 1.49 x 10-4, a =0.82
Gel Permeation Chromatography:
GPC separates based on the
size or hydrodynamic volume
The smaller analytes can enter the pores more easily and therefore spend more time in these
pores, increasing their retention time. These smaller molecules spend more time in the column
and therefore will elute last. Conversely, larger analytes spend little if any time in the pores and
are eluted quickly. All columns have a range of molecular weights that can be separated.
Wikipedia
GPC Separation of Free-Radical Synthesized
GPC Separation of Anionically
Polystyrene; Mn=24,000 g/mol, PDI=4.96
Synthesized Polystyrene; Mn=3,000 g/mol,
PDI=1.32
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6969EN%20GPC%20SEC%20Chrom%20Guide.pdf
Page 4-11
Read:
Billmeyer
P16 D
P 19 Practice problem 3
Chapter 8
Abbreviati Polymer Name
on
ABS Acrylonitrile-butadiene-styrene
HDPE High density polyethylene
HIPS High impact polystyrene
LDPE Low-density polyethylene
PA Polyamide
PAA Poly acrylic acid
PAN Polyacrylonitrile
PC Polycarbonate
PE Polyethylene
PEEK Polyetheretherketone
PET Poly(ethylene terephthalate)
PF Phenol-formaldehyde resin
PMMA Polymethyl methacrylate
PP Polypropylene
PS Polystyrene
PTFE Polytetrafluoroethylene
PVC Poly(vinyl chloride)
SAN Styrene-acrylonitrile plastic
UF Urea-formaldehyde resin
UHMWPE Ultra-high molecular weight PE
Polymer Classification
Thermoplastic-undergoes reversible deformation
Thermoset-stable to heat and cannot be made to
flow or melt
Polymerization
Chain-growth(addition) polymerization
Pi + M Pi+1
Pi + Pj Pi+j
Step-growth (condensation) polymerization
Pi + M Pi+j + L
Pi + Pj Pi+j + L
P: polmer; M: monomer; L: leaving group; i, j 1
Addition Polymerization
CH2 CH CH2 CH CH2 CH
+
Cl Cl Cl 2
CH2 CH CH2 CH
CH2 CH +
Cl Cl 2+n
Cl 2
CH2 CH CH2 CH
CH2 CH
+ Cl m Cl m+n
Cl n
Condensation Polymerization
HOCH2OH + Cl-OC(CH2)8CO-Cl HOCH2OCO(CH2)8COCl + HCl
OCH2OCO(CH2)8CO + OCH2OCO(CH2)8CO OCH2OCO(CH2)8CO
m n m+n
+ HCl
