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1
H &
13
C Nuclear Magnetic Resonance
spectroscopy (NMR)
Infrared spectroscopy (Fourier
Transform IR)
Elemental or combustion analyses
Molecular weight
Polymerization Techniques
Bulk-no solvent just monomer +
catalysts
Solution Polymerization-in solvent
Suspension-micron-millimeter spheres
Emulsion-ultrasmall spheres
Bulk Polymerizations
Rare
Overheat & explode with scale up
No solvent-just monomer
Polymer usually vitrifies before done
Broad MW distribution
Acrylic sheets by Bulk polymerization of MMA
Storage of vinyl monomers in air = peroxide
initiated polymerizations
Tankcar of styrene
2005 in Ohio
Solution Polymerization
Better control of reaction temperature
Better control of polymerization
Slower
Not very green-residual solvent
Suspension Polymerization
Oil droplets dispersed in water
Initiator soluble in oil
Greener than solution polymerization
Filter off particles of polymer
Emulsion
Polymerization
Still oil in water (or the reverse)
Initiator in water
Smaller particles (latex)
Excellent control of temp
Solution turns white
Polystyrene latex
Suspension Emulsion Mini-emulsion Micro-emulsion
Monomer in oil Monomer in oil Monomer in oil Monomer in oil
Initiator in oil Initiator in water Initiator in water Initiator in water
Less Common Polymerization
Techniques
Solid state polymerization
Polymerization of crystalline monomers
Diacetylene crystals
Gas Phase polymerization
Parylene polymerizations
Plasma polymerization
Put anything in a plasma
Solid State Polymerizations
Heating Oligomeric Condensation
Polymers
T
g
< X < T
m
Nylons, Polyesters
O
O
O
O
O
HO O
O
O
n
O
O
O
O
O
O O
O
O
n
OH
250 C
HO
OH
Nylon 66 T
g
= 70 C and T
m
= 264
C
T
g
= 67 C and T
m
= 265 C
Solid State Polymerizations
Topological Polymerizations: Polymerization of crystals
Quinodimethane polymerizations
Di- and Triacetylene polymerizations
In single crystals
Solid State Polymerizations of Fullerenes
Topological polymerization in 3-D
Gas Phase Polymerization
1) Light olefins
2) Parylenes
LIGHT OLEFINS
Ethylene and propylene
2004 Global PE Demand: 136 Billion Pounds
Food Packaging
Hygiene & Medical
Consumer & Ind. Liners
Stretch Films
Agricultural Films
HDSS
Film
SOURCE: Nexant/ChemSystems 2005, PTAI 1/05
Types of Polyethylene
O
O
O
O
O
O
O
O
O
O
C-OH
O
HDPE (0.940-0.965)
High Density
LLDPE (0.860-0.926)
Linear Low Density
LDPE (0.915-0.930)
Low Density
High Pressure Copolymers
(AA, VA, MA, EA)
Gas Phase Polymerization: Light olefins
Oxygen initiator
2-3K atmospheres
250 C
Gas Phase Polymerization: Light olefins
Fluidized bed polymerization
MORE
FLEXIBLE
Gas Phase Polymerization: Paralene
Gas phase
Polymerizes on contact
Conformal coatings
Pinhole free
Preserving artifacts (paper)
Microelectronics
Medical devices
Plasma Polymerization
500 - 1 micron thick films
Continuous coatings
Solvent free
High cohesion to surface
Highly cross-linked
Generally amorphous
Plasma Polymerization
Monomers: Hydrocarbons
Double or triple bonds nice, not necessary
Fluorocarbon
Tetraalkoxysilanes (for silica)
P- pumps; PS-power supply; S-substrate
M-feed gas inlet; G-vacuum gauge
Fig1. Bell-jar type reactors
Fig 2. Tubular-type reactors
Plasma Polymerization
Plasma Polymerization
PET [Poly(Ethylene Terephthalate)]
Multi-layer bottles
No loss of fizz
Characterization of Polymers
1
H &
13
C Nuclear Magnetic Resonance
spectroscopy (NMR)
Infrared spectroscopy (Fourier
Transform IR)
Elemental or combustion analyses
Molecular weight
13
C NMR is a very powerful way to determine
the microstructure of a polymer.
13
C NMR shift is sensitive to the two
stereocenters on either side on sptectrometers
> 300 MHz. This is called pentad resolution.
r m m r m r
mmrm pentad
m = meso (same orientation)
r = racemic (opposite orientation)
1 2 1 2
13
C NMR spectrum of CH
3
region of atactic polypropylene
Infrared Spectroscopy: Bond vibrations
2-16 Micron wavelength range
polystyrene
C=C-H
C-H
C=C
stretch
Infrared Spectroscopy: Bond vibrations
Poly(methyl methacrylate)
C=O
C-O
C-H
stretch
C-H bend
Types of Addition Polymerizations
Ph
Anionic
C
3
H
7
Li
C
4
H
9
Ph
Li
+
Ph
n
C
4
H
9
Ph Ph
Li
+
n
Ph
Radical
PhCO
2
Ph
n
Ph
Cationic
Cl
3
Al OH
2
H
Ph
HOAlCl
3
Ph
n
H
Ph Ph
n
HOAlCl
3
PhCO
2
Ph
PhCO
2
Ph Ph
n
Chemical Modification of Polymers
1) Hydrolysis
2) Oxidation
3) Photochemistry
(can be oxidation or not)
4) Chemical crosslinking
5) Chemical modification
O
O
CH
3
n NaOH
H
2
O
OH
n
O
O
H
3
C
n
Na
+
Polyvinylacetate
polyvinyl alcohol
O
n
H
Poly ethylene oxide
hv, O
2
or ascorbic
acid
Me
O
H
Si
Si
Si
Si
Si
R
R
R R
R R
R
R
R
R
Polysilane
hv: UV
O
2
Si
O
Si O
Si
O
Si O
R
R
R
R
R
R
R
R
H
polybutadiene
S
8
A
S
S
S
See next slide
Chemical Modification of Polyvinyl Alcohol to make
Polyvinyl butyral for safety glass
polyvinyl alcohol
OH OH OH OH OH
CH
3
CH
2
CH
2
CHO
O O OH O O
poly vinyl butyral
No PVB
With PVB
Bullet Proof Glass
glass, laminates and polycarbonate
sheets are interlaid in a clean room to
ensure clarity. In our large autoclave,
superheated steam seals the layers
together.
Making bullet proof glass
Polycarbonate is
Strong Material
Young's modulus (E) 2-2.4 Gpa
Tensile strength (t) 55-75 Mpa
Exploding CDs
Mythbusters:
> 23,000 rpm CD will shatter
Scratches or defects are the culprit
52X drive -MAX: 27,500 rpm
typical: 11,000 rpm
10,000 RPM = 65 m/s = 145 mph
7200 gravities of acceleration
And approx. 5 MPa stress
Yield Strength 60 MPa
Nalgene
Polycarbonate Properties
Density: 1.2 g/cc
Young's modulus (E) 2-2.4 Gpa
Tensile strength (t) 55-75 Mpa
Elongation () @ break 80-150%
Glass transition (Tg) 150 C
Melting (Tm) 267 C
Upper working temperature 115-130 C
$7.3-11/kg
Bisphenol and Endocrine System
100-250 g bisphenol per Liter water in water bottles
20 g/Liter per day can disrupt mouse development
vom Saal, F.S., Richter, C.A., Ruhlen, R.R. Nagel, S.C. and Welshons, W.V. Disruption of laboratory
experiments due to leaching of bisphenol a from polycarbonate cages and bottles and uncontrolled
variability in components of animal feed. Proceedings from the International Workshop on
Development of Science-Based Guidelines for Laboratory Animal Care, National Academies Press,
Washington DC, 65-69, 2004.
Immune system
Antioxidant enzymes
Decreases plasma testosterone
Learning disabilities
vom Saal, F.S., Nagel, S.C., Timms, B.G. and Welshons, W.V. Implications for human health of the extensive
bisphenol A literature showing adverse effects at low doses: A response to attempts to mislead the public.
Toxicology, 212:244-252, 2005.
Nalgene Substitutes-food and water
Glass (blender, pitchers, glasses)
Metal (water bottles)
Polyethylene (water bottles)
Polyamide or Nylon (baby bottles)