chapter 2c office hours: tuesday 1pm monday & wednesday 12-1 or e-mail for an appointment old...
TRANSCRIPT
![Page 1: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/1.jpg)
Chapter 2c
Office hours: Tuesday 1pmMonday & Wednesday 12-1or e-mail for an appointmentOld Chem 309
Bibliography due on Friday 11:59 PMUpload file on D2L.
![Page 2: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/2.jpg)
Polymerization Techniques
• Bulk-no solvent just monomer + catalysts
• Solution Polymerization-in solvent
• Suspension-micron-millimeter spheres
• Emulsion-ultrasmall spheres
![Page 3: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/3.jpg)
Bulk Polymerizations
RareOverheat & explode with scale upNo solvent-just monomerPolymer usually vitrifies before doneBroad MW distribution
Acrylic sheets by Bulk polymerization of MMA
![Page 4: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/4.jpg)
Storage of vinyl monomers in air = peroxide initiated polymerizations
Tankcar of styrene2005 in Ohio
![Page 5: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/5.jpg)
Solution Polymerization • Better control of reaction temperature• Better control of polymerization• Slower• Not very green-residual solvent
![Page 6: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/6.jpg)
Suspension Polymerization
• Oil droplets dispersed in water
• Initiator soluble in oil
• Greener than solution polymerization
Filter off particles of polymer
![Page 7: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/7.jpg)
Emulsion Polymerization
Still oil in water (or the reverse)Initiator in waterSmaller particles (latex)Excellent control of tempSolution turns white
Polystyrene latex
![Page 8: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/8.jpg)
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 waterInitiator in water
![Page 9: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/9.jpg)
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
![Page 10: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/10.jpg)
Solid State Polymerizations
Heating Oligomeric Condensation Polymers
Tg < X < Tm
Nylons, Polyesters
O
O
O
O
O
HO O
O
O
n
O
O
O
O
O
O O
O
On
OH
250 °C
HOOH
Nylon 66 Tg = 70 °C and Tm = 264 °C
Tg = 67 °C and Tm = 265 °C
![Page 11: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/11.jpg)
Solid State Polymerizations
Topological Polymerizations: Polymerization of crystals
Quinodimethane polymerizations
Di- and Triacetylene polymerizationsIn single crystals
![Page 12: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/12.jpg)
Solid State Polymerizations of Fullerenes
Topological polymerization in 3-D
![Page 13: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/13.jpg)
Gas Phase Polymerization
1) Light olefins2) Parylenes
![Page 14: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/14.jpg)
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
![Page 15: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/15.jpg)
Types of Polyethylene
O
OOO
O O
OO
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)
![Page 16: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/16.jpg)
Gas Phase Polymerization: Light olefins
Oxygen initiator2-3K atmospheres250 °C
![Page 17: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/17.jpg)
Gas Phase Polymerization: Light olefins
Fluidized bed polymerization
MORE FLEXIBLE
![Page 18: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/18.jpg)
Gas Phase Polymerization: Paralene
Gas phasePolymerizes on contactConformal coatingsPinhole freePreserving artifacts (paper)MicroelectronicsMedical devices
![Page 19: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/19.jpg)
Plasma Polymerization
•500 Å - 1 micron thick films•Continuous coatings•Solvent free•High cohesion to surface•Highly cross-linked•Generally amorphous
![Page 20: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/20.jpg)
Plasma Polymerization
Monomers: HydrocarbonsDouble or triple bonds nice, not necessaryFluorocarbonTetraalkoxysilanes (for silica)
![Page 21: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/21.jpg)
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
![Page 22: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/22.jpg)
Plasma Polymerization
PET [Poly(Ethylene Terephthalate)]Multi-layer bottlesNo loss of fizz
![Page 23: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/23.jpg)
Characterization of Polymers
• 1H & 13C Nuclear Magnetic Resonance spectroscopy (NMR)
• Infrared spectroscopy (Fourier Transform IR)
• Elemental or combustion analyses
• Molecular weight
![Page 24: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/24.jpg)
13C NMR is a very powerful way to determine the microstructure of a polymer.
13C NMR shift is sensitive to the two stereocenters on either side on sptectrometers > 300 MHz. This is called pentad resolution.
r mm rmr
mmrm pentad
m = meso (same orientation)r = racemic (opposite orientation)
12 1 2
13C NMR spectrum of CH3 region of atactic polypropylene
![Page 25: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/25.jpg)
Infrared Spectroscopy: Bond vibrations
2-16 Micron wavelength range
polystyreneC=C-H
C-H
C=Cstretch
![Page 26: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/26.jpg)
Infrared Spectroscopy: Bond vibrations
Poly(methyl methacrylate)
C=O
C-O
C-Hstretch
C-H bend
![Page 27: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/27.jpg)
Types of Addition Polymerizations
Ph
Anionic
C3H7 Li C4H9
Ph
Li+ Phn
C4H9
Ph Ph
Li+
n
Ph
Radical
PhCO2•Ph
n
Ph
Cationic
Cl3Al OH2H
PhHOAlCl3
Phn
H
Ph Phn
HOAlCl3
PhCO2
PhPhCO2
Ph Phn
![Page 28: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/28.jpg)
Chemical Modification of Polymers
1) Hydrolysis
2) Oxidation
3) Photochemistry (can be oxidation or not)
4) Chemical crosslinking
5) Chemical modification
O
OCH3
n NaOH
H2O OHn
O
O
H3Cn
Na+
Polyvinylacetate polyvinyl alcohol
On
H
Poly ethylene oxidehv, O2
or ascorbic acid
Me
O
H
SiSi
SiSi
SiR R
R R
R R
R R
R R
Polysilane
hν: UV
O2
SiOSi O
SiO
SiO
R RR
R
RR
R
R
H
polybutadiene
S8
Δ SS
S
See next slide
![Page 29: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/29.jpg)
Chemical Modification of Polyvinyl Alcohol to make Polyvinyl butyral for safety glass
polyvinyl alcohol
OH OH OH OH OH
CH3CH2CH2CHO
O O OH O O
poly vinyl butyral
No PVB
With PVB
![Page 30: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/30.jpg)
Bullet Proof Glass
![Page 31: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/31.jpg)
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
![Page 32: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/32.jpg)
Polycarbonate is Strong Material
Young's modulus (E) 2-2.4 Gpa
Tensile strength (σt) 55-75 Mpa
![Page 33: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/33.jpg)
Exploding CD’s
Mythbusters:> 23,000 rpm CD will shatterScratches or defects are the culprit
52X drive -MAX: 27,500 rpm typical: 11,000 rpm
10,000 RPM = 65 m/s = 145 mph7200 gravities of accelerationAnd approx. 5 MPa stressYield Strength 60 MPa
![Page 34: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/34.jpg)
Nalgene
![Page 35: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/35.jpg)
Polycarbonate Properties
Density: 1.2 g/cc
Young's modulus (E) 2-2.4 Gpa
Tensile strength (σt) 55-75 Mpa
Elongation (ε) @ break 80-150%
Glass transition (Tg) 150 °C
Melting (Tm) 267 °C
Upper working temperature 115-130 °C
$7.3-11/kg
![Page 36: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/36.jpg)
Bisphenol and Endocrine System
100-250 g bisphenol per Liter water in water bottles20 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 systemAntioxidant enzymesDecreases plasma testosteroneLearning 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.
![Page 37: Chapter 2c Office hours: Tuesday 1pm Monday & Wednesday 12-1 or e-mail for an appointment Old Chem 309 daloy@mse.arizona.edu Bibliography due on Friday](https://reader036.vdocuments.mx/reader036/viewer/2022062716/56649dc95503460f94abfca5/html5/thumbnails/37.jpg)
Nalgene Substitutes-food and water
• Glass (blender, pitchers, glasses)
• Metal (water bottles)
• Polyethylene (water bottles)
• Polyamide or Nylon (baby bottles)