ChE #1:
Engineering Polymers:
How Plastics are
Made
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Plexiglas, or
Polymethyl Methacrylate
(PMMA)
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A “Bubble Chair”
An Aquarium
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PMMA Properties
Extremely transparent.
Hard & Shatterproof.
Thermoplastic: mold, melt, &
remold again.
Highly weather resistant.
Doesn’t yellow over time.
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PMMA Production
 Made in sheets, rods, tubes, or beads.
 Methyl Methacrylate(MMA) + Initiator.
 Benzoyl Peroxide(BP).
 Principles of Polymer Systems. Rodriguez et al.
 PMMA sheet: bulk polymerization
in a
batch reactor(BR)
sheet mold.
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PMMA REACTOR DESIGN
We calculated that 100 aquariums (15L each) require
740kg of PMMA to make.
Polymerization
t:54 hrs
MMA +
Benzoyl
Peroxide
T=60°C
740kg
PMMA
Reactor Volume=780L
Mold @ t=0
MMA: 9.43 mol/L
BP:1.0x10-7 mol/L
Mold @ t=54hrs
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Polyether Ether Ketone (PEEK)
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Polyether ether ketone (PEEK)
An advanced engineering plastic
High resistance to abrasion, chemicals, fire,
hydrolysis, and radiation
Applications: aviation, automobile, manufacturing,
electronic apparatuses, and food and beverage
industries
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PEEK in Comparison to other
Plastics
Superior ductility
High electrical
resistance
Low moisture
absorption
High thermal
resistance
http://www.quadrantplastics.com/na-en/products/injection-moldedsolutions/working-together/material-selection.html
High Young’s
Modulus
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Sulfonation of PEEK
H2SO4
Sulfonated PEEK (SPEEK) has improved solubility
that allows it to be subjected to size exclusion
chromatography, which gives it a better molar mass
distribution
Compared to the original PEEK, SPEEK has a longer
molecular chain, which gives it superior mechanical
properties
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Reaction Kinetics




 C0 
1


ln    ln
  k3  k 2  ( 2 k t )  k 2  (  k t ) 
 Ct 
e 2  
e 3 
 
  k3  2k 2 

 k 3  2k 2 
Source: Mechanism and kinetics of poly(ether ether ketone) sulfonation in concentrated sulfuric acid at room temperature by D
Daoust, J Devaux, and P Godard
Where C0 is the initial concentration and Ct is the concentration at
reaction time t of the unsulfonated –OфO– groups, and k2 and k3 are the
apparent rate constants at 20°C shown below:
Concentrations of
sulfuric acid (wt %)
ka(h-1)
k2
k3
95.9
4.9x10-3
2.7x10-3
96.8
7.2x10-3
3.2x10-3
97.7
19.3x10-3
10.3x10-3
98.6
48.0x10-3
19.8x10-3
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Results
97.7% of H2SO4 @ 20°C and a goal of 99.9%
sulfonation: 26.4 days (extremely long time)
98.6% H2SO4 @ 20°C and a goal of 99%
sulfonation: 8.7 days (shorter, but still very
long time)
Thus, the relatively shorter time to run the
batch to sulfonate PEEK would be 8.7 days
within 98.6% H2SO4 and 99% sulfonation
May be possible to increase the speed with
increased temperature
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Introduction
• Polyacetal/Polyformaldehyde
• Monomer: Formaldehyde
HISTORY
• 1920: Staudinger unsuccessfully researched
• 1959: Delrin (POM) introduced into the market
MARKET
• Global Demand: 808 kt
• Price: $1.29 – $1.38/ lb
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Main Properties
•
•
•
•
•
•
•
Wear Resistant
Impact Resistant
Moisture Resistant
Resistant to Most Organic Solvents
High Creep Resistant
Resistant to Low Temperatures
Low Friction Coefficient
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Uses
Buckles
Conveyor Belt
Gears
Snowboard Buckles
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Production Process
Carbon monoxide
methanol
formaldehyde
Carbon Monoxide + Hydrogen produce methanol
Methanol oxidizes to form formaldehyde
Formaldehyde chain polymerizes to
polyoxymethylene
Solution Polymerization (Solvent: Heptane)
Insoluble Polymer
polyoxymethylene
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Air
34,000 kg
Production Process
of Formaldehyde
Reactor 1 : Silver
Catalyst
Vaporizer
Reactor 2: Copper
Catalyst
2,800 kg
Water
Methanol
5000 kg
Polymerization
reactor
1 million
POM
Gears
Air Compressor
Valve
Heat exchanger
Pure
Formaldehyde
4,000 kg
Water
+
Methanol
Distillation
System
Absorber
CO2 Methyl Formate
335 kg
13kg
U.S. Patent: 6,147,263
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Polyphthalamide (PPA)
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Polyphthalamide (PPA)
• Comprised of HMD, TPA, IPA, and adipic acid.
Hexamethylenediamine
Terephthalic acid
• Raw material: Castor
bean plant
• Used to make PA10T
type of PPA
Isophthalic acid
Adipic acid
• Provides the diamine
portion of the polymer
• Renewable resource
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Properties
Uses
• high T
• automotive
resistance
components
• chemical
• plumbing
resistance
• electronic
• low creep
connectors
• harmless
• MetaCork
to the body • lamp sockets
• flexible
• fuel system
• dimensionally components
stable
Oica.com (accessed July 19, 2011). “World Motor Vehicle Production by Country and
Type”.
• Demand has increased
with the increase of
production of motor
vehicles (Desirable
alternative to metal)
• $2.72-3.18 per lb
(fairly high price)
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Polymerization Reactor Design
• Interfacial
• Multiple reactors involved to
polycondensation reaction
achieve a high molecular
weight of between 1000 g/mol
• Solution polymerization
and 3000 g/mol
(aqueous)
• Batch reactor
Batch reactor
• Results: Multiple 2.14 L
reactors running for 13.5
hours (based on Malluche et
al., Polymer Engineering and
Science, 2007)
• Predicted design not very
efficient, likely to switch to
a different reactor
configuration
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POLYCARBONATE (PC)
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POLYCARBONATE (PC)
- PC is a high quality
engineering plastic.
- PC was invented by Dr. Fox
and Dr. Schnell in 1953.
- A thermoplastic that has
excellent heat resistance
good electrical insulation
properties
high transparency.
Figure 1: PC has a high impact strength compared to those
of other plastics
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THERE IS PC ALL AROUND US
PC is found in:
-bottles
-CDs & DVDs
-tableware
-containers
-electrical shavers
-cell phone cases
-computers
-vehicle lights
-tubes
-sheets
-food mixers
-glasses
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THE DEMAND FOR POLYCARBONATE
-In 2011, America’s
demand for
polycarbonate reached
1,780 million pounds.
-From 1995 to
2011 there was a
large increase in
the demand
(1,320 million
pounds of PC)
(Source: The Freedonia Group, Inc. “Polycarbonate demand to increase 5.2 percent
annually” http://www.theiapdmagazine.com ©The Freedonia Group, Inc. 2002.)
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PRODUCTION PROCESS
Polymerization Mechanism: Step Growth
Figure 3: Direct phosgenation (left) and
transesterification (right) methods
Type Of Polymerization: Bulk
Polymerization
Methods of Production:
-Direct Phosgenation
-Transesterification
Materials Used For Direct Phosgenation:
-Bisphenol A (BPA)
-Phosgene
Materials Used For Transesterification:
-Bisphenol A (BPA)
(Source: Green Industry“Examples of Safer Reactions”
-Dimethyl Carbonate
http://www.greener industry.org.uk.)
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BULK POLYMERIZATION IN A BATCH
REACTOR
 The overall objective is to design a
batch reactor to produce a specified
amount of polycarbonate via the
transesterification of DPC with BPA.
 Both the volume of the reactor and
the time required to run the reactor
are essential to design a chemical
plant.
Figure 4: This is a diagram of a
bulk polymerization
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SPORTS BOTTLE PRODUCTION
Make 1000 Sports Bottles: (450,000 g)
TIME REQUIRED TO RUN A
REACTOR:
 
DPC 
x0
dx
x 4kr x 20  8kr x0 x  4kr  k f x 2


(Rate Constants were obtained from Hersh, and Choi., J. Appl.
Polym. Sci., 1990)
-It takes 0.34-0.71 seconds depending
on the target chain length, which is
really fast.
VOLUME OF THE
REACTOR:
VPC = VDPC +VBPA =
WDPC WBPA
+
rDPC rBPA
- The volume for the
reactor would be 390 L.
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Kevlar
Poly(para-phenylene terephthalamide)
PPTA
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Applications and Properties
• Bulletproof vests
• Car tires
• Ropes and cables
•
•
•
•
High tensile strength
Lightweight
Flexible
Flame-resistant
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Synthesis and Production
•
•
•
•
Para-phenylenediamine
Terephthaloyl chloride
Condensation reaction
Polymer is spun into fibers, then woven into fabric
PPD
TCL
Kevlar
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Reactor Design and Optimization
• Highly reactive and exothermic → solution polymerization
• Stirred batch reactor with a cooling water jacket
N batches per day
Batch reactor downtime
• Cleaning tank
• Filling tank for next batch
N(t + td) = 86,400 seconds
td = aV + b
Thermodynamic data: Zhang, Tao, et al. A novel scalable synthesis process of PPTA by coupling n-pentane evaporation for polymerization
heat removal. Chinese Chemical Letters, 2011.
Kinetic data: Gupta, J.S., et al. Polymerization Kinetics of Rodlike Molecules under Quiescent Conditions. AIChE Journal , 2001, 1, p. 177.
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Reactor Design and Optimization
For 30 bulletproof vests per day
(~10,000 per year):
•
•
•
•
90 kg of Kevlar
N = 8 batches per day
V = 11,000 L
t = 3800 s (~1 hr)
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By Nika Sabasteanski and George Kaufer
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-Feedstock: Lactic Acid
Lactide (isomers)
-Polymerization: Ring Opening Polymerization
-Benefits
-Biodegradable
Figure 1:
Yogurt
-Applications
containers
-Biomedical: Sutures
-Food: Yogurt containers
-Market
-Cargill Dow Nature Works
-Projections: 7% growth per year
Figure 2: Sutures
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Production Process
-Production
-Bulk Polymerization
-Batch Reactor
-Volume ≈ 2,400 L
-Synthesis: Chain Growth
Figure 3: Synthesis
-Initiator, Catalysts
-Found Information
-Kinetic Parameters (used in program)
-Chemical Properties
-Method of Solution
-MATLAB: Euler’s Method
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MATLAB Program for Reactor Design
clear all
format long
%Clears all stored variables
%Displays numbers at double precision
D = 0.02;
N = 500;
kp=0.901;
ki=1;
kt=1*10^-6;
%Step size in minutes
%Number of steps
%l/mol*min
%l/mol*min
%l/mol*min
M0=9.16;
M=zeros(1,N);
M(1)=M0;
%Found initial concentration by dividing density of L-Lactide by the
molecular weight of L-Lactide, L/mol
%Initialize array of monomer concentrations
%Picking the inital value of M to be M0
I0=1*10^-8;
I=zeros(1,N);
I(1)=I0;
%L/mol, chosen
%Initialize array of initator concentrations
%Picking the inital value of I to be I0
P=zeros(1,N);
P(1)=(kp*M0)/((kp*M0)+(2*kt*ki*I0*M0)^.5);
t0 = 0;
t=zeros(1,N);
t(1)=t0;
%Initial time in minutes
%Initialize array of times
%Picking the inital value of t to be t0
for i = 1:N
dmdt = -kp*M(i)*(((ki/kt)*I(i)*M(i))^.5);
didt=-ki*I(i)*M(i);
t(i+1)=t(i)+D;
M(i+1)=M(i)+D*dmdt;
I(i+1)=I(i)+D*didt;
P(i+1)=(kp*M(i+1))/(kp*M(i+1)+((2*kt*ki*I(i+1)*M(i+1))^.5));
end
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Emissions and Byproducts
-Emission
-Byproduct
-Carbon Dioxide
-Normal Butanol (n-butanol)
Figure 4: Carbon Dioxide Emissions
from leading plastics
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THANK YOU VERY MUCH
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