ChE #1: Engineering Polymers: How Plastics are Made The Cooper
Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Slide 2 Polymethyl Methacrylate (PMMA)
Plexiglas, or The Cooper Union for the Advancement of Science and
Art Summer Research Internship Program 2011 Slide 3 A Bubble
ChairAn Aquarium The Cooper Union for the Advancement of Science
and Art Summer Research Internship Program 2011 Slide 4 PMMA
Properties Extremely transparent. Hard & Shatterproof.
Thermoplastic: mold, melt, & remold again. Highly weather
resistant. Doesnt yellow over time. The Cooper Union for the
Advancement of Science and Art Summer Research Internship Program
2011 Slide 5 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. The Cooper Union
for the Advancement of Science and Art Summer Research Internship
Program 2011 Slide 6 PMMA REACTOR DESIGN The Cooper Union for the
Advancement of Science and Art Summer Research Internship Program
2011 740kg PMMA Polymerization t:54 hrs T=60 C Reactor Volume=780L
Mold @ t=0Mold @ t=54hrs We calculated that 100 aquariums (15L
each) require 740kg of PMMA to make. MMA: 9.43 mol/L BP:1.0x10 -7
mol/L MMA + Benzoyl Peroxide Slide 7 Polyether Ether Ketone (PEEK)
The Cooper Union for the Advancement of Science and Art Summer
Research Internship Program 2011 Slide 8 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 The Cooper Union for the Advancement of Science
and Art Summer Research Internship Program 2011 Slide 9 PEEK in
Comparison to other Plastics The Cooper Union for the Advancement
of Science and Art Summer Research Internship Program 2011 Superior
ductility High electrical resistance Low moisture absorption High
thermal resistance High Youngs Modulus
http://www.quadrantplastics.com/na-en/products/injection-molded-
solutions/working-together/material-selection.html Slide 10
Sulfonation of PEEK 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 The Cooper Union for the Advancement
of Science and Art Summer Research Internship Program 2011 H 2 SO 4
Slide 11 Reaction Kinetics The Cooper Union for the Advancement of
Science and Art Summer Research Internship Program 2011 Where C 0
is the initial concentration and C t is the concentration at
reaction time t of the unsulfonated OO groups, and k 2 and k 3 are
the apparent rate constants at 20C shown below: Concentrations of
sulfuric acid (wt %)k2k2 95.94.9x10 -3 2.7x10 -3 96.87.2x10 -3
3.2x10 -3 97.719.3x10 -3 10.3x10 -3 98.648.0x10 -3 19.8x10 -3 k a
(h -1 ) k3k3 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 Slide 12 Results
97.7% of H 2 SO 4 @ 20C and a goal of 99.9% sulfonation: 26.4 days
(extremely long time) 98.6% H 2 SO 4 @ 20C 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% H 2 SO 4 and 99% sulfonation May be possible
to increase the speed with increased temperature The Cooper Union
for the Advancement of Science and Art Summer Research Internship
Program 2011 Slide 13 Slide 14 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
The Cooper Union for the Advancement of Science and Art Summer
Research Internship Program 2011 Slide 15 Wear Resistant Impact
Resistant Moisture Resistant Resistant to Most Organic Solvents
High Creep Resistant Resistant to Low Temperatures Low Friction
Coefficient The Cooper Union for the Advancement of Science and Art
Summer Research Internship Program 2011 Slide 16 Uses The Cooper
Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Conveyor Belt Gears Buckles Snowboard
Buckles Slide 17 Production Process Carbon Monoxide + Hydrogen
produce methanol Methanol oxidizes to form formaldehyde
Formaldehyde chain polymerizes to polyoxymethylene Solution
Polymerization (Solvent: Heptane) Insoluble Polymer The Cooper
Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Carbon monoxide methanol formaldehyde
polyoxymethylene Slide 18 Vaporizer Reactor 1 : Silver Catalyst
Reactor 2: Copper Catalyst Distillation System CO 2 335 kg 2,800 kg
Water + Methanol 5000 kg Pure Formaldehyde 4,000 kg Air 34,000 kg
Production Process of Formaldehyde Methyl Formate 13kg Absorber 1
million POM Gears Polymerization reactor The Cooper Union for the
Advancement of Science and Art Summer Research Internship Program
2011 Air Compressor Valve U.S. Patent: 6,147,263 Heat exchanger
Slide 19 The Cooper Union for the Advancement of Science and Art
Summer Research Internship Program 2011 Polyphthalamide (PPA) Slide
20 The Cooper Union for the Advancement of Science and Art Summer
Research Internship Program 2011 Comprised of HMD, TPA, IPA, and
adipic acid. Raw material: Castor bean plant Used to make PA10T
type of PPA Terephthalic acid Isophthalic acid Adipic acid
Hexamethylenediamine Provides the diamine portion of the polymer
Renewable resource Slide 21 Properties high T resistance chemical
resistance low creep harmless to the body flexible dimensionally
stable Uses automotive components plumbing electronic connectors
MetaCork lamp sockets fuel system components Demand has increased
with the increase of production of motor vehicles (Desirable
alternative to metal) $2.72-3.18 per lb (fairly high price) The
Cooper Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Oica.com (accessed July 19, 2011). World
Motor Vehicle Production by Country and Type. Slide 22 Interfacial
polycondensation reaction Solution polymerization (aqueous) Batch
reactor Multiple reactors involved to achieve a high molecular
weight of between 1000 g/mol and 3000 g/mol 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
Polymerization Reactor Design Batch reactor The Cooper Union for
the Advancement of Science and Art Summer Research Internship
Program 2011 Slide 23 POLYCARBONATE (PC) Slide 24 -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.
POLYCARBONATE (PC) Figure 1: PC has a high impact strength compared
to those of other plastics The Cooper Union for the Advancement of
Science and Art Summer Research Internship Program 2011 Slide 25
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 The
Cooper Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Slide 26 THE DEMAND FOR POLYCARBONATE The
Cooper Union for the Advancement of Science and Art Summer Research
Internship Program 2011 -In 2011, Americas 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.) Slide 27 Polymerization Mechanism: Step Growth 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) -Dimethyl Carbonate
PRODUCTION PROCESS Figure 3: Direct phosgenation (left) and
transesterification (right) methods The Cooper Union for the
Advancement of Science and Art Summer Research Internship Program
2011 ( Source: Green IndustryExamples of Safer Reactions
http://www.greener industry.org.uk.) Slide 28 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 The Cooper Union for the Advancement of Science and
Art Summer Research Internship Program 2011 Slide 29 TIME REQUIRED
TO RUN A REACTOR: VOLUME OF THE REACTOR: Make 1000 Sports Bottles:
(450,000 g) -It takes 0.34-0.71 seconds depending on the target
chain length, which is really fast. - The volume for the reactor
would be 390 L. (Rate Constants were obtained from Hersh, and
Choi., J. Appl. Polym. Sci., 1990) SPORTS BOTTLE PRODUCTION The
Cooper Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Slide 30 Kevlar The Cooper Union for the
Advancement of Science and Art Summer Research Internship Program
2011 Poly(para-phenylene terephthalamide) PPTA Slide 31
Applications and Properties High tensile strength Lightweight
Flexible Flame-resistant Bulletproof vests Car tires Ropes and
cables The Cooper Union for the Advancement of Science and Art
Summer Research Internship Program 2011 Slide 32 Synthesis and
Production The Cooper Union for the Advancement of Science and Art
Summer Research Internship Program 2011 PPDTCL Kevlar
Para-phenylenediamine Terephthaloyl chloride Condensation reaction
Polymer is spun into fibers, then woven into fabric Slide 33
Reactor Design and Optimization Highly reactive and exothermic
solution polymerization Stirred batch reactor with a cooling water
jacket The Cooper Union for the Advancement of Science and Art
Summer Research Internship Program 2011 Batch reactor downtime
Cleaning tank Filling tank for next batch N batches per dayN(t + t
d ) = 86,400 seconds t d = 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. Slide 34 Reactor Design
and Optimization The Cooper Union for the Advancement of Science
and Art Summer Research Internship Program 2011 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) Slide 35 The Cooper Union for
the Advancement of Science and Art Summer Research Internship
Program 2011 By Nika Sabasteanski and George Kaufer Slide 36 The
Cooper Union for the Advancement of Science and Art Summer Research
Internship Program 2011 - Feedstock: Lactic Acid Lactide (isomers)
- Polymerization: Ring Opening Polymerization - Benefits
-Biodegradable - Applications -Biomedical: Sutures -Food: Yogurt
containers - Market -Cargill Dow Nature Works -Projections: 7%
growth per year Figure 1: Yogurt containers Figure 2: Sutures Slide
37 Production Process -Production -Bulk Polymerization -Batch
Reactor -Volume 2,400 L -Synthesis: Chain Growth -Initiator,
Catalysts -Found Information -Kinetic Parameters (used in program)
-Chemical Properties -Method of Solution -MATLAB: Eulers Method The
Cooper Union for the Advancement of Science and Art Summer Research
Internship Program 2011 Figure 3: Synthesis Slide 38 clear all
%Clears all stored variables format long %Displays numbers at
double precision D = 0.02; %Step size in minutes N = 500; %Number
of steps kp=0.901; %l/mol*min ki=1; %l/mol*min kt=1*10^-6;
%l/mol*min M0=9.16; %Found initial concentration by dividing
density of L-Lactide by the molecular weight of L-Lactide, L/mol
M=zeros(1,N); %Initialize array of monomer concentrations M(1)=M0;
%Picking the inital value of M to be M0 I0=1*10^-8; %L/mol, chosen
I=zeros(1,N); %Initialize array of initator concentrations I(1)=I0;
%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; %Initial time in
minutes t=zeros(1,N); %Initialize array of times t(1)=t0; %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
MATLAB Program for Reactor Design The Cooper Union for the
Advancement of Science and Art Summer Research Internship Program
2011 Slide 39 Emissions and Byproducts -Emission -Carbon Dioxide
The Cooper Union for the Advancement of Science and Art Summer
Research Internship Program 2011 Figure 4: Carbon Dioxide Emissions
from leading plastics -Byproduct -Normal Butanol (n-butanol) Slide
40 THANK YOU VERY MUCH The Cooper Union for the Advancement of
Science and Art Summer Research Internship Program 2011
