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ChE #1: Engineering Polymers: How Plastics are Made The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011.

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Presentation on theme: "ChE #1: Engineering Polymers: How Plastics are Made The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011."— Presentation transcript:

1 ChE #1: Engineering Polymers: How Plastics are Made The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

2 Polymethyl Methacrylate (PMMA) Plexiglas, or The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

3 A “Bubble Chair”An Aquarium The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

4 PMMA Properties  Extremely transparent.  Hard & Shatterproof.  Thermoplastic: mold, melt, & remold again.  Highly weather resistant.  Doesn’t yellow over time. The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

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

6 PMMA REACTOR DESIGN The Cooper Union for the Advancement of Science and Art Summer Research Internship Program kg PMMA Polymerization t:54 hrs T=60 °C Reactor Volume=780L 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

7 Polyether Ether Ketone (PEEK) The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011

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

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 Young’s Modulus solutions/working-together/material-selection.html

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

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 –OфO– groups, and k 2 and k 3 are the apparent rate constants at 20°C shown below: Concentrations of sulfuric acid (wt %)k2k x x x x x x x x10 -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

12 Results  97.7% of H 2 SO 20°C and a goal of 99.9% sulfonation: 26.4 days (extremely long time)  98.6% H 2 SO 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% 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

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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

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

16 Uses The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011 Conveyor Belt Gears Buckles Snowboard Buckles

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

18 Vaporizer Reactor 1 : Silver Catalyst Reactor 2: Copper Catalyst Distillation System CO 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

19 The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011 Polyphthalamide (PPA)

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

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) $ 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”.

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

23 POLYCARBONATE (PC)

24 -PC is a high quality engineering plastic. -PC was invented by Dr. Fox and Dr. Schnell in 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

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

26 THE DEMAND FOR POLYCARBONATE The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 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” ©The Freedonia Group, Inc )

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 Industry“Examples of Safer Reactions” industry.org.uk.)

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

29 TIME REQUIRED TO RUN A REACTOR: VOLUME OF THE REACTOR: Make 1000 Sports Bottles: (450,000 g) -It takes 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

30 Kevlar The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011 Poly(para-phenylene terephthalamide) PPTA

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

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

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, Kinetic data: Gupta, J.S., et al. Polymerization Kinetics of Rodlike Molecules under Quiescent Conditions. AIChE Journal, 2001, 1, p. 177.

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)

35 The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011 By Nika Sabasteanski and George Kaufer

36 The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 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

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: Euler’s Method The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011 Figure 3: Synthesis

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

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)

40 THANK YOU VERY MUCH The Cooper Union for the Advancement of Science and Art Summer Research Internship Program 2011


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